Gallium-aluminum-phosphorus-silicon-oxide molecular sieve compositions

ABSTRACT

Molecular sieve compositions having three-dimensional microporous framework structures of GaO 2 , AlO 2 , PO 2  and SiO 2  tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula: 
     
         mR: (Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 
    
     wherein &#34;R&#34; represents at least one organic templating agent present in the intracrystalline pore system; &#34;m&#34; represents the molar amount of &#34;R&#34; present per mole of (Ga w  Al x  P y  Si z )O 2  ; and &#34;w&#34;, &#34;x&#34;, &#34;y&#34; and &#34;z&#34; represent the mole fractions of gallium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

This application is a continuation-in-part of our copending applicationSer. No. 599,925 filed Apr. 13, 1984, now abandoned.

FIELD OF THE INVENTION

The instant invention relates to a novel class of crystallinemicroporous molecular sieves and to the method of their preparation. Theinvention relates to novel gallium-aluminum-phosphorus-silicon-oxidemolecular sieves containing framework tetrahedral oxide units ofgallium, aluminum, phosphorus and silicon. These compositions may beprepared hydrothermally from gels containing reactive compounds ofgallium, aluminum, phosphorus and silicon capable of forming frameworktetrahedral oxides, and preferably at least one organic templating agentwhich function in part to determine the course of the crystallizationmechanism and the structure of the crystalline product.

BACKGROUND OF THE INVENTION

Molecular sieves of the crystalline aluminosilicate zeolite type arewell known in the art and now comprise over 150 species of bothnaturally occurring and synthetic compositions. In general thecrystalline zeolites are formed from corner-sharing AlO₂ and SiO₂tetrahedra and are characterized by having pore openings of uniformdimensions, having a significant ion-exchange capacity and being capableof reversibly desorbing an adsorbed phase which is dispersed throughoutthe internal voids of the crystal without displacing any atoms whichmake up the permanent crystal structure. Other crystalline microporouscompositions which are not zeolitic, i.e. do not contain AlO₂ tetrahedraas essential framework constituents, but which exhibit the ion-exchangeand/or adsorption characteristics of the zeolites are also known. Metalorganosilicates which are said to possess ion-exchange properties, haveuniform pores and are capable of reversibly adsorbing molecules havingmolecular diameters of about 6 Å or less, are reported in U.S. Pat. No.3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph,silicalite, having molecular sieving properties and a neutral frameworkcontaining neither cations nor cation sites is disclosed in U.S. Pat.No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.

A recently reported class of microporous compositions and the firstframework oxide molecular sieves synthesized without silica, are thecrystalline aluminophosphate compositions disclosed in U.S. Pat. No.4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials areformed from AlO₂ and PO₂ tetrahedra and have electrovalently neutralframeworks as in the case of silica polymorphs. Unlike the silicamolecular sieve, silicalite, which is hydrophobic due to the absence ofextra-structural cations, the aluminophosphate molecular sieves aremoderately hydrophilic, apparently due to the difference inelectronegativity between aluminum and phosphorus. Theirintracrystalline pore volumes and pore diameters are comparable to thoseknown for zeolites and silica molecular sieves.

In U.S. Pat. No. 4,440,871, there is described a novel class ofsilicon-substituted aluminophosphates which are both microporous andcrystalline. The materials have a three dimensional crystal framework ofPO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units and, exclusive of any alkalimetal or calcium which may optionally be present, an as-synthesizedempirical chemical composition on an anhydrous basis of:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, the maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular silicoaluminophosphate species involved;and "x", "y", and "z" represent the mole fractions of silicon, aluminumand phosphorus, respectively, present as tetrahedral oxides. The minimumvalue for each of "x", "y", and "z" is 0.01 and preferably 0.02. Themaximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52.These silicoaluminophosphates exhibit several physical and chemicalproperties which are characteristic of aluminosilicate zeolites andaluminophosphates.

In U.S. Pat. No. 4,500,651, there is described a novel class oftitanium-containing molecular sieves whose chemical composition in theas-synthesized and anhydrous form is represented by the unit empiricalformula:

    mR:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Ti_(x) Al_(y) P_(z))O₂ and has a value of betweenzero and about 5.0; and "x", "y" and "z" represent the mole fractions oftitanium, aluminum and phosphorus, respectively, present as tetrahedraloxides.

In U.S. Pat. No. 4,567,029, there is described a novel class ofcrystalline metal aluminophosphates having three-dimensional microporousframework structures of MO₂, AlO₂ and PO₂ tetrahedral units and havingan empirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; "M" represents at least one metal of the group magnesium,manganese, zinc and cobalt; "x", "y", and "z" represent the molefractions of the metal "M", aluminum and phosphorus, respectively,present as tetrahedral oxides.

In U.S. Pat. No. 4,544,143, there is described a novel class ofcrystalline ferroaluminophosphates having a three-dimensionalmicroporous framework structure of FeO₂, AlO₂ and PO₂ tetrahedral unitsand having an empirical chemical composition on an anhydrous basisexpressed by the formula

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; and "x", "y" and "z" represent the mole fractions of the iron,aluminum and phosphorus, respectively, present as tetrahedral oxides.

The instant invention relates to new molecular sieve compositionscomprising framework tetrahedral units of GaO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ andSiO₂.

DESCRIPTION OF THE FIGURES

FIG. 1 is a ternary diagram wherein parameters relating to the instantcompositions are set forth as mole fractions.

FIG. 2 is a ternary diagram wherein parameters relating to preferredcompositions are set forth as mole fractions.

FIG. 3 is a ternary diagram wherein parameters relating to the reactionmixtures employed in the preparation of the compositions of thisinvention are set forth as mole fractions.

SUMMARY OF THE INVENTION

The instant invention relates to a new class ofgallium-aluminum-phosphorus-silicon-oxide molecular sieves having acrystal framework structure of GaO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral oxide units. These new molecular sieves exhibition-exchange, adsorption and catalytic properties and, accordingly, findwide use as adsorbents and catalysts. The members of this novel class ofcompositions have crystal framework structures of GaO₂ ⁻, AlO₂ ⁻, PO₂ ⁺and SiO₂ tetrahedral units and have an empirical chemical composition onan anhydrous basis expressed by the formula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of gallium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides. These molecular sieve compositionscomprise crystalline molecular sieves having a three-dimensionalmicroporous framework structure of GaO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral units.

The instant molecular sieve compositions are characterized in severalways as distinct from heretofore known molecular sieves, including theaforementioned ternary compositions. The instant molecular sieves arecharacterized by the enhanced thermal stability of certain species andby the existence of species heretofore unknown for binary and ternarymolecular sieves.

The molecular sieves of the instant invention will be generally referredto by the acronym "GaAPSO" to designate the framework of GaO₂ ⁻, AlO₂ ⁻,PO₂ ⁺ and SiO₂ tetrahedral units. Actual class members will beidentified by denominating the various structural species which make upthe GaAPSO class by assigning a number and, accordingly, are identifiedas "GaAPSO-i" wherein "i" is an integer. This designation is anarbitrary one and is not intended to denote structural relationship toanother material(s) which may also be characterized by a numberingsystem.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to a new class ofgallium-aluminum-phosphorus-silicon-oxide molecular sieves comprising acrystal framework structure of GaO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral oxide units. These new molecular sieves exhibition-exchange, adsorption and catalytic properties and, accordingly, findwide use as adsorbents and catalysts.

The GaAPSO molecular sieves of the instant invention comprise aframework structure of GaO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral unitshaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than about 0.2; and"w", "x", "y" and "z" represent the mole fractions of gallium, aluminum,phosphorus and silicon, respectively, present as tetrahedral oxides. Themole fractions "w", "x", "y" and "z" are generally defined as beingwithin the pentagonal compositional area defined by points A, B, C, Dand E of the ternary diagram of FIG. 1. Points A, B, C, D and E of FIG.1 have the following values for "w", "x", "y", and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z + w                                           ______________________________________                                        A        0.60          0.38   0.02                                            B        0.38          0.60   0.02                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the GaAPSO molecular sieves the values of"w", "x", "y" and "z" in the above formula are within the hexagonalcompositional area defined by the points a, b, c, d, e and f of theternary diagram which is FIG. 2 of the drawings, said points a, b, c, d,e and f representing the following values for "w", "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z + w                                           ______________________________________                                        a        0.60          0.38   0.02                                            b        0.38          0.60   0.02                                            c        0.01          0.60   0.39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

In an especially preferred subclass of the GaAPSO molecular sieves thevalues of "w", "x", "y" and "z" in the above formula are within thehexagonal compositional area defined by the points g, h, i, j, k and lof the ternary diagram which is FIG. 2 of the drawings, said points g,h, i, j, k and l representing the following values for "w", "x", "y" and"z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z + w                                           ______________________________________                                        g        0.45          0.40   0.15                                            h        0.33          0.52   0.15                                            i        0.20          0.52   0.28                                            j        0.20          0.45   0.35                                            k        0.36          0.29   0.35                                            l        0.45          0.29   0.26                                            ______________________________________                                    

The GaAPSOs of this invention are useful as adsorbents, catalysts,ion-exchangers, and the like in much the same fashion asaluminosilicates have been employed heretofore, although their chemicaland physical properties are not necessarily similar to those observedfor aluminosilicates.

GaAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofgallium, aluminum, phosphorus and silicon, preferably an organictemplating, i.e., structure-directing agent, preferably a compound of anelement of Group VA of the Periodic Table, and/or optionally an alkalior other metal. The reaction mixture is generally placed in a sealedpressure vessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenouspressure, at a temperature between 50° C. and 250° C., and preferablybetween 100° C. and 200° C., until crystals of the GaAPSO product areobtained, usually for a period of from several hours to several weeks.Effective crystallization times of from about 2 hours to about 30 daysare generally employed with from about 4 hours to about 20 days, andpreferably about 2 to about 15 days, being typically employed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the GaAPSO compositions of the instant invention, it ispreferred to employ a reaction mixture composition expressed in terms ofthe molar ratios as follows:

    aR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and desirably not greater than 1.0; "b" has a value of fromzero (0) to about 500, preferably between about 2 and about 300, mostpreferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of gallium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01. In apreferred embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe pentagonal compositional area defined by points F, G, H, I and J ofthe ternary diagram of FIG. 3. Points F, G, H, I and J of FIG. 3 havethe following values for "w", "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        F        0.60          0.38   0.02                                            G        0.38          0.60   0.02                                            H        0.01          0.60   0.39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.5 to 1.0 total moles of gallium and silicon, and from about 0.75 toabout 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x" "y" and "z" suchthat (w+x+y+z)=1.00 mole, whereas in the examples the reaction mixturesare expressed in terms of molar oxide ratios normalized to the moles ofAl₂ O₃ and/or P₂ O₅. This latter form is readily converted to the formerform by routine calculations by dividing the number of moles of eachcomponent (including the template and water) by the total number ofmoles of gallium, aluminum, phosphorus and silicon which results innormalized mole fractions based on total moles of the aforementionedcomponents.

In forming reaction mixtures from which the instant molecular sieves areformed the organic templating agent can be any of those heretoforeproposed for use in the synthesis of conventional zeolitealuminosilicates. In general these compounds contain elements of GroupVA of the Periodic Table of Elements, particularly nitrogen, phosphorus,arsenic and antimony, preferably nitrogen or phosphorus and mostpreferably nitrogen, which compounds also contain at least one alkyl oraryl group having from 1 to 8 carbon atoms. Particularly preferredcompounds for use as templating agents are the amines, quarternaryphosphonium and quaternary ammonium compounds, the latter two beingrepresented generally by the formula R₄ X⁺ wherein "X" is phosphorus ornitrogen and each R is an alkyl or aryl group consisting from 1 to 8carbon atoms. Polymeric quaternary ammonium salts such as [(C₁₄ H₃₂N₂)(OH)₂ ]_(x) wherein "x" has a value of at least 2 are also suitablyemployed. The mono-, di- and tri-amines are advantageously utilized,either alone or in combination with a quaternary ammonium compound orother templating compound. Mixtures of two or more templating agents caneither produce mixtures of the desired GaAPSOs or the more stronglydirecting templating species may control the course of the reaction withthe other templating species serving primarily to establish the pHconditions of the reaction gel. Representative templating agents includetetramethylammonium; tetraethylammonium; tetrapropylammonium; andtetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine;tripropylamine; triethylamine; triethanolamine; piperidine;cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine;N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine;1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine,N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Notevery templating agent will direct the formation of every species ofGaAPSO, i.e., a single templating agent can, with proper manipulation ofthe reaction conditions, direct the formation of several GaAPSOcompositions, and a given GaAPSO composition can be produced usingseveral different templating agents.

The reactive phosphorus source is preferably phosphoric acid, butorganic phosphates such as triethyl phosphate have been foundsatisfactory, and so also have crystalline or amorphousaluminophosphates such as the AlPO₄ composition of U.S. Pat. No.4,310,440. Organo-phosphorus compounds, such as tetrabutylphosphoniumbromide, do not, apparently, serve as reactive sources of phosphorus,but these compounds do function as templating agents. Conventionalphosphorus salts, such as sodium metaphosphate, may be used, at least inpart, as the phosphorus source, but are not preferred.

Almost any reactive silicon source may be employed such that SiO₂tetrahedral units are formed in situ. The reactive silicon source may besilica in the form of a silica sol, may be a fumed silica or may beother conventional sources of silica used in zeolite synthesis such asreactive solid amorphous precipitated silicas, silica gel, alkoxides ofsilicon, tetraalkyl orthosilicates (for example, tetraethylorthosilicate), silicic acid, alkali metal silicates and the like.

The preferred aluminum source is either an aluminum alkoxide, such asaluminum isoproproxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

The reactive source of gallium can be introduced into the reactionsystem in any form which permits the formation in situ of a reactiveform of gallium, i.e., reactive to form the framework tetrahedral oxideunit of gallium. Compounds of gallium which may be employed includeoxides, alkoxides, hydroxides, chlorides, bromides, iodides, sulfates,nitrates, carboxylates (e.g., acetates) and the like.

While not essential to the synthesis of GaAPSO compositions, stirring orother moderate agitation of the reaction mixture and/or seeding thereaction mixture with seed crystals of either the GaAPSO species to beproduced or a topologically similar aluminophosphate, aluminosilicate ormolecular sieve composition, facilitates the crystallization procedure.

After crystallization the GaAPSO product may be isolated andadvantageously washed with water and dried in air. The as-synthesizedGaAPSO generally contains within its internal pore system at least oneform of the templating agent employed in its formation. Most commonlythe organic moiety derived from an organic template is present, at leastin part, as a charge-balancing cation as is generally the case withas-synthesized aluminosilicate zeolites prepared from organic-containingreaction systems. It is possible, however, that some or all of theorganic moiety is an occluded molecular species in a particular GaAPSOspecies. As a general rule the templating agent, and hence the occludedorganic species, is too large to move freely through the pore system ofthe GaAPSO product and must be removed by calcining the GaAPSO attemperatures of 200° C. to 700° C., and preferably 350° C. to 600° C.,to thermally degrade the organic species. In a few instances the poresof the GaAPSO product are sufficiently large to permit transport of thetemplating agent, particularly if the latter is a small molecule, andaccordingly complete or partial removal thereof can be accomplished byconventional desorption procedures such as are carried out in the caseof zeolites. It will be understood that the term "as-synthesized" asused herein does not include the condition of the GaAPSO phase whereinthe organic moiety occupying the intracrystalline pore system as aresult of the hydrothermal crystalline process has been reduced bypost-synthesis treatment such that the value of "m" in the compositionformula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an alkoxide isemployed as the source of gallium, aluminum, phosphorus and/or silicon,the corresponding alcohol is necessarily present in the reaction mixturesince it is a hydrolysis product of the alkoxide. It has not beendetermined whether this alcohol participates in the synthesis process asa templating agent. For the purposes of this application, however, thisalcohol is arbitrarily omitted from the class of templating agents, evenif it is present in the as-synthesized GaAPSO material.

Since the present GaAPSO compositions are formed from GaO₂, AlO₂, PO₂and SiO₂ tetrahedral units which, respectively, have a net charge of -1,-1, +1 and 0, the matter of cation exchangeability is considerably morecomplicated than in the case of zeolite molecular sieves in which,ideally, there is a stoichiometric relationship between AlO₂ ⁻tetrahedra and charge-balancing cations. In the instant compositions, anAlO₂ ⁻ tetrahedron can be balanced electrically either by associationwith a PO₂ ⁻ tetrahedron or a simple cation such as an alkali metalcation, a cation of gallium present in the reaction mixture, a proton(H⁺), or an organic cation derived from the templating agent. Similarly,a GaO₂ ⁻ tetrahedron can be balanced electrically by association withPO₂ ⁺ tetrahedra, a cation of gallium present in the reaction mixture, asimple cation such as an alkali metal cation, a proton (H⁺), organiccations derived from the templating agent, or other divalent orpolyvalent metal cations introduced from an extraneous source. It hasalso been postulated that non-adjacent AlO₂ ⁻ and PO₂ ⁺ tetrahedralpairs can be balanced by Na⁺ and OH- respectively [Flanigen and Grose,Molecular Sieve Zeolites-I, ACS, Washington DC (1971)].

The GaAPSO compositions of the present invention may exhibitcation-exchange capacity when analyzed using ion-exchange techniquesheretofore employed with zeolitic aluminosilicates and have porediameters which are inherent in the lattice structure of each speciesand which are at least about 3 Å in diameter. Ion exchange of GaAPSOcompositions is ordinarily possible only after the organic moietypresent as a result of synthesis has been removed from the pore system.Dehydration to remove water present in the as-synthesized GaAPSOcompositions can usually be accomplished, to some degree at least, inthe usual manner without removal of the organic moiety, but the absenceof the organic species greatly facilitates adsorption and desorptionprocedures. The GaAPSO materials will have various degrees ofhydrothermal and thermal stability, some being quite remarkable in thisregard, and will function as molecular sieve adsorbents and hydrocarbonconversion catalysts or catalyst bases.

In preparing the GaAPSO composition it is preferred to use a stainlesssteel reaction vessel lined with an inert plastic material, e.g.,polytetrafluoroethylene, to avoid contamination of the reaction mixture.In general, the final reaction mixture from which each GaAPSOcomposition is crystallized is prepared by forming mixtures of less thanall of the reagents and thereafter incorporating into these mixturesadditional reagents either singly or in the form of other intermediatemixtures of two or more reagents. In some instances the reagents admixedretain their identity in the intermediate mixture and in other casessome or all of the reagents are involved in chemical reactions toproduce new reagents. The term "mixture" is applied in both cases.Further, it is preferred that the intermediate mixtures as well as thefinal reaction mixtures be stirred until substantially homogeneous.

X-ray patterns of reaction products are obtained by X-ray analysis,using standard X-ray powder diffraction techniques. The radiation sourceis a high-intensity, copper target, X-ray tube operated at 50 Kv and 40ma. The diffraction pattern from the copper K-alpha radiation andgraphite monochromator is suitably recorded by an X-ray spectrometerscintillation counter, pulse height analyzer and strip chart recorder.Flat compressed powder samples are scanned at 2θ (2 theta) per minute,using a two second time constant. Interplanar spacings (d) in Angstromunits are obtained from the position of the diffraction peaks expressedas 2θ where θ is the Bragg angle as observed on the strip chart.Intensities were determined from the heights of diffraction peaks aftersubtracting background, "I_(o) " being the intensity of the strongestline or peak, and "I" being the intensity of each of the other peaks.Alternatively, the X-ray patterns may be obtained by use of computerbased techniques using copper K-alpha radiation, Siemens type K-805X-ray sources and Siemens D-500 X-ray powder diffractometers availablefrom Siemens Corporation, Cherry Hill, N.J.

As will be understood by those skilled in the art, the determination ofthe parameter 2 theta is subject to both human and mechanical error,which in combination, can impose an uncertainty of about ±0.4° on eachreported value of 2 theta. This uncertainty is, of course, alsomanifested in the reported values of the d-spacings, which arecalculated from the 2 theta values. This imprecision is generalthroughout the art and is not sufficient to preclude the differentiationof the present crystalline materials from each other and from thecompositions of the prior art. In some of the X-ray patterns reported,the relative intensities of the d-spacings are indicated by thenotations vs, s, m, w and vw which represent very strong, strong,medium, weak and very weak, respectively.

In certain instances hereinafter in the illustrative examples, thepurity of a synthesized product may be assessed with reference to itsX-ray powder diffraction pattern. Thus, for example, if a sample isstated to be pure, it is intended only that the X-ray pattern of thesample is free of lines attributable to crystalline impurities, not thatthere are no amorphous materials present.

The molecular sieves of the instant invention may be characterized bytheir X-ray powder diffraction patterns and such may have one of theX-ray patterns set forth in the following Tables A through X, whereinsaid X-ray patterns are for the as-synthesized form unless otherwisenoted. In most cases, the pattern of the corresponding calcined formwill also fall within the relevant table. However, in some cases theremoval of the occluded templating agent which occurs during calcinationwill be accompanied by sufficient relaxation of the lattice to shiftsome of the lines slightly outside the ranges specified in the relevanttable. In a small number of cases, calcination appears to cause moresubstantial distortion in the crystal lattice, and hence, moresignificant changes in the X-ray powder diffraction pattern.

                  TABLE A                                                         ______________________________________                                        (GaAPSO-5)                                                                    2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-7.7      12.28-11.48                                                                             m-vs                                                   19.4-19.9    4.58-4.46 w-m                                                    20.85-21.3   4.26-4.17 w-vs                                                   22.1-22.6    4.02-3.93 m-vs                                                   25.6-26.2    3.480-3.402                                                                             vw-m                                                   ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        (GaAPSO-11)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.8-8.2      11.19-10.85                                                                             m-s .sup.                                              9.0-9.8      9.83-9.03 vw-vs .sup.                                            12.8-13.6    6.92-6.51 vw-m                                                   19.9-20.5    4.46-4.33 m-s .sup.                                              20.8-21.8    4.27-4.08 m-vs                                                   22.0-22.6    4.04-3.93 m-vs                                                   22.6-23.1    3.93-3.85 vw-vs .sup.                                            23.1-23.5    3.85-3.79 w-vs                                                   ______________________________________                                    

                  TABLE C                                                         ______________________________________                                        (GaAPSO-14)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                         8.6-8.9     10.3-9.93                                                                              vs                                                      13.0         6.81     w                                                       21.9-22.2    4.06-4.00                                                                              w                                                       25.4         3.51     w                                                       27.5         3.24     w                                                       29.7         3.01     w                                                       ______________________________________                                    

                  TABLE D                                                         ______________________________________                                        (GaAPSO-16)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        11.3-11.6    7.83-7.63  w-vs                                                  18.55-18.9   4.78-4.70 vw-m .sup.                                             21.85-22.2   4.07-4.00  m-vs                                                  22.8-23.3    3.900-3.818                                                                             w-m                                                    26.4-27.3    3.370-3.267                                                                             w-m                                                    29.6-29.9    3.018-2.988                                                                             w-m                                                    ______________________________________                                    

                  TABLE E                                                         ______________________________________                                        (GaAPSO-17)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.70-7.75    11.5-11.4 vs                                                     13.4         6.61       s-vs                                                   15.5-15.55  5.72-5.70 s                                                      19.65-19.7   4.52-4.51 w-s                                                    20.5-20.6    4.33-4.31 vs                                                     31.8-32.0    2.812-2.797                                                                             w-s                                                    ______________________________________                                    

                  TABLE F                                                         ______________________________________                                        (GaAPSO-18)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                         9.6-9.65    9.21-9.16 vs                                                      15.5-15.55  5.72-5.70 m                                                      16.9-17.1    5.25-5.19 m                                                      20.15-20.25  4.41-4.39 m                                                      20.95-21.05  4.24-4.22 m                                                      31.8-32.5    2.814-2.755                                                                             m                                                      ______________________________________                                    

                  TABLE G                                                         ______________________________________                                        (GaASPO-20)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.8-14.2    6.42-6.23 m-vs                                                    19.6-20.15  6.53-4.41 m                                                      24.1-24.8    3.695-3.603                                                                             m-vs                                                   27.9-28.6    3.198-3.121                                                                             w                                                      31.3-32.1    2.861-2.791                                                                             w                                                      34.35-35.0   2.610-2.601                                                                             w-m                                                    ______________________________________                                    

                  TABLE H                                                         ______________________________________                                        (GaAPSO-31)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.4-9.5      10.53-9.31                                                                              w-s                                                    20.2-20.4    4.40-4.35 m                                                      22.0-22.1    4.040-4.022                                                                             m                                                      22.5-22.7    3.952-3.92                                                                              vs                                                     31.6-31.8    2.831-2.814                                                                             w-m                                                    ______________________________________                                    

                  TABLE J*                                                        ______________________________________                                        (GaAPSO-33)                                                                   2θ      d(Å) Relative Intensity                                     ______________________________________                                        9.25-9.55     9.56-9.26                                                                              w-m                                                    12.5-12.9     7.08-6.86                                                                              vs                                                     16.9-17.3     5.25-5.13                                                                              w-m                                                    20.45-20.9    4.34-4.25                                                                              w-m                                                    23.85-24.25   3.73-3.67                                                                              w-m                                                    26.05-26.35   3.42-3.38                                                                              w-m                                                    27.3-27.6     3.27-3.23                                                                              vs                                                     ______________________________________                                         *as-synthesized form                                                     

                  TABLE K*                                                        ______________________________________                                         (GaAPSO-33)                                                                  2θ      d(Å) Relative Intensity                                     ______________________________________                                        13.15-13.4    6.73-6.61                                                                              vs                                                     18.05-18.35   4.91-4.83                                                                              m                                                      18.4-18.6     4.82-4.77                                                                              m                                                      26.55-26.7    3.36-3.34                                                                              m                                                      32.0-32.1     2.80-2.79                                                                              m                                                      ______________________________________                                         *calcined form                                                           

                  TABLE L                                                         ______________________________________                                        (GaAPSO-34)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.3-9.8      9.51-9.03   m-vs                                                 12.6-13.2    7.03-6.71  .sup. w-m                                             15.8-16.3    5.61-5.44 vw-m                                                   20.25-21.2   4.39-4.19   w-vs                                                 24.8-25.4     3.59-3.507                                                                             vw-m                                                   30.0-30.9    2.979-2.894                                                                             vw-m                                                   ______________________________________                                    

                  TABLE M                                                         ______________________________________                                        (GaAPSO-35)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        10.6-11.1    8.35-7.97 vw-vs                                                  13.1-13.7    6.76-6.46 vw-vs                                                  17.0-17.6    5.22-5.04 w-s                                                    20.6-21.6    4.31-4.11 vw-m                                                   21.6-22.3    4.11-3.99 .sup.  m-vs                                            28.1-28.8    3.175-3.100                                                                             vw-m                                                   ______________________________________                                    

                  TABLE N                                                         ______________________________________                                        (GaAPSO-36)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.45-8.0     11.14-11.05                                                                             vs                                                     8.1-8.3      10.91-10.65                                                                             w-m                                                    16.3-16.6    5.44-5.34 w-m                                                    18.9-19.4    4.70-4.57 w-m                                                    20.7-21.0    4.29-4.23 w-m                                                    ______________________________________                                    

                  TABLE O                                                         ______________________________________                                        (GaAPSO-37)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        6.1-6.3      14.49-14.03                                                                             vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE P                                                         ______________________________________                                        (GaAPSO-39)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m                                                      13.1-13.5    6.76-6.56 m                                                      17.8-18.4    4.98-4.82 w-m                                                    20.8-21.3    4.27-4.17  m-vs                                                   22.2-22.85   4.00-3.892                                                                              m-vs                                                   26.4-27.05  3.376-3.296                                                                             w-m                                                    ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (GaAPSO-40)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.5-7.7      11.79-11.48                                                                             vw-m .sup.                                             8.0-8.1      11.05-10.94                                                                             .sup.  s-vs                                            12.4-12.5    7.14-7.08  w-vs                                                  13.6-13.8    6.51-6.42 m-s                                                    14.0-14.1    6.33-6.28 w-m                                                    27.8-28.0    3.209-3.187                                                                             w-m                                                    ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (GaAPSO-41)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.6-13.8    6.51-6.42 w-m                                                    20.5-2.6     4.33-4.31 w-m                                                    21.1-21.3    4.21-4.17 vs                                                     22.1-22.3    4.02-3.99 m-s                                                    22.8-23.0    3.90-3.86 m                                                      23.1-23.4    3.82-3.80 w-m                                                    25.5-25.9    3.493-3.44                                                                              w-m                                                    ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (GaAPSO-42)                                                                   2θ      d(Å)  Relative Intensity                                    ______________________________________                                        7.15-7.4      12.36-11.95                                                                              .sup. m-vs                                            12.5-12.7    7.08-6.97 m-s                                                   21.75-21.9    4.09-4.06 m-s                                                    24.1-24.25   3.69-3.67 vs                                                    27.25-27.4    3.273-3.255                                                                             s                                                      30.05-30.25  2.974-2.955                                                                             m-s                                                   ______________________________________                                    

                  TABLE T                                                         ______________________________________                                        (GaAPSO-43)                                                                   2θ      d(Å)  Relative Intensity                                    ______________________________________                                        12.3-12.95    7.20-6.83 m-vs                                                  16.8-17.45    5.28-5.09 vw-w                                                  21.45-21.85   4.145-4.071                                                                             m-vs                                                  27.1-27.85    3.291-3.232                                                                             w-vs                                                  32.4-33.2     2.763-2.699                                                                             vw-m                                                  ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (GaAPSO-44)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m-vs                                                   15.9-16.3    5.57-5.44 vw-m                                                   20.5-21.0    4.33-4.23 m-vs                                                   24.3-25.1     3.66-3.548                                                                             w-m                                                    30.5-31.1    2.931-2.876                                                                             vw-m                                                   ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        (GaAPSO-46)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-8.1      12.28-10.92                                                                             vs                                                     12.9-13.6    6.86-6.51 vw                                                     21.2-22.2     4.19-4.501                                                                             vw-m                                                    22.5-23.45   3.95-3.793                                                                             vw-m                                                   26.6-27.9    3.351-3.198                                                                             vw-m                                                   ______________________________________                                    

                  TABLE W                                                         ______________________________________                                        (GaAPSO-47)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.4-9.6      9.41-9.21 vs                                                     12.8-13.1    6.92-6.76 vw-m                                                   16.0-16.3    5.54-5.44 vw-m                                                   20.5-21.0    4.31-4.23   m-vs                                                 24.6-25.3    3.613-3.526                                                                             vw-m                                                   30.6-31.1    2.921-2.876                                                                             vw-m                                                   ______________________________________                                    

                  TABLE X                                                         ______________________________________                                        (GaAPSO-26)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                         8.2         10.8-10.7                                                                              vs                                                      10.5-10.6    8.45-8.42                                                                              vw-w                                                    15.2         5.84     w                                                       17.7-17.8    5.00-4.99                                                                              vw-w                                                    21.8         4.07     w                                                       22.4         3.97-3.96                                                                              .sup.  w-m                                              ______________________________________                                    

The following examples are provided to further illustrate the inventionand are not intended to be limiting thereof:

EXAMPLE 1 Preparation of GaAPSO-5

A mixture was formed by combining 5.1 grams of 85 wt. percentorthophosphoric acid (H₃ PO₄) with 8.4 grams of water and adding to theresultant solution 2.5 grams of hydrated aluminum oxide in the form of apseudo-boemite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt.percent of H₂ O. The resultant mixture was stirred until homogeneous.This homogeneous mixture was combined with a second mixture prepared byadding 0.9 grams of a fumed silica (94.1 wt percent) SiO₂, 5.9 wt.percent H₂ O) to a solution containing 1.3 grams of gallium(III)hydroxide (86.4 wt. percent Ga₂ O₃, 13.6 wt. percent H₂ O) dissolved in18.1 grams of 40 wt. percent aqueous tetraethylammonium hydroxide(TEAOH), and the combined mixtures were stirred until homogeneous. Thecomposition of the final reaction mixture thus produced, expressed interms of the molar oxide ratios of the components of the reactionmixture, was:

2.0TEAOH:0.25Ga₂ O₃ :0.75Al₂ O₃ :0.6SiO₂ :0.90P₂ O₅ :50H₂ O.

An aliquot of this final reaction mixture was digested by sealing it ina stainless steel pressure vessel lined with polytetrafluoroethylene andheating it in an oven at 150° C. under autogenous pressure for 95 hours.The solid reaction product (which was determined by the analysesdescribed below to be mainly GaAPSO-5) was recovered by centrifugation,washed with water and dried in air at ambient temperatures.

The X-ray powder diffraction pattern of the major product, assynthesized, was characterized by the data in the following Table AA:

                  TABLE AA                                                        ______________________________________                                        (GaAPSO-5)                                                                                         Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         7.5         11.8    100                                                      12.9         6.84    10                                                       13.0         6.81    10                                                       19.9         4.45    44                                                       21.3         4.17    34                                                       22.6         3.93    61                                                       24.8         3.60     3                                                       26.2         3.41    22                                                       29.3         3.05    11                                                       30.3          2.947  18                                                       33.9          2.645   6                                                       34.5          2.599   6                                                       34.8          2.577  12                                                       38.1          2.362   7                                                       ______________________________________                                    

EXAMPLE 2 Preparation of GaAPSO-11

(a) GaAPSO-11 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0DPA:0.05-0.2Ga₂ O₃ :0.5-1.0 Al₂ O₃ :0.5-1.0P₂ O₅ :0.1-0.6SiO₂:40-100H₂ O

where "DPA" denotes di-n-propylamine.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce GaAPSO-11 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The GaAPSO-11 product's chemical analysis shows the GaAPSO-11 productcontains gallium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a GaAPSO-11 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.8-8.2      11.19-10.85                                                                             m-s .sup.                                              9.0-9.8      9.83-9.03 vw-vs .sup.                                            12.8-13.6    6.92-6.51 vw-m.sup.                                              19.9-20.5    4.46-4.33 m-s .sup.                                              20.8-21.8    4.27-4.08 m-vs                                                   22.0-22.6    4.04-3.93 m-vs                                                   22.6-23.1    3.93-3.85 vw-vs .sup.                                            23.1-23.5    3.85-3.79 w-vs                                                   ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined GaAPSO-11 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined GaAPSO-11 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric absorptionapparatus the measurements are made on a sample after activation at 350°C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    5                                        O.sub.2  3.46       750      -183    6                                        Cyclohexane                                                                            6.0        90       24      4                                        H.sub.2 O                                                                              2.65       4.3      24      6                                        H.sub.2 O                                                                              2.65       20       24      8                                        ______________________________________                                         *Typical amount adsorbed                                                 

The pore diameter of GaAPSO-11 is about 6 Å.

EXAMPLE 3 Preparation of GaAPSO-17

(a) GaAPSO-17 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0QN:0.05-0.2Ga₂ O₃ :0.5-1.0Al₂ O₃ :0.5-1.0P₂ O₅ :0.1-0.6SiO₂:40-100H₂ O

where "QN" denotes quinuclidine.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce GaAPSO-17 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The GaAPSO-17 product's chemical analysis shows the GaAPSO-17 productcontains gallium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a GaAPSO-17 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.70-7.75    11.5-11.4 vs                                                     13.4         6.61         s-vs                                                 15.5-15.55  5.72-5.70  .sup. s                                               19.65-19.7   4.52-4.51 w-s                                                    20.5-20.6    4.33-4.31 vs                                                     31.8-32.0    2.812-2.797                                                                             w-s                                                    ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined GaAPSO-17 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined GaAPSO-17 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    10                                       O.sub.2  3.46       750      -183    12                                       n-Butane 4.3        100      24      4                                        H.sub.2 O                                                                              2.65       4.3      24      13                                       H.sub.2 O                                                                              2.65       20       24      14                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of GaAPSO-17 is about 4.3 Å.

EXAMPLE 4 Preparation of GaAPSO-31

(a) GaAPSO-31 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0 DPA:0.05-0.2Ga₂ O₃ :0.5-1.0Al₂ O₃ :0.5-1.0P₂ O₅ :0.1-0.6SiO₂:40-100H₂ O

where "DPA" denotes di-n-propylamine.

The reaction mixture is seeded with crystals of AlPO₄ -31 (U.S. Pat. No.4,310,440) and digested by placing the reaction mixture in a sealedstainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce GaAPSO-31 product.Solids awe then recovered by filtration, washed with water and dried inair at room temperature.

The GaAPSO-31 product's chemical analysis shows the GaAPSO-31 productcontains gallium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a GaAPSO-31 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.4-9.5      10.53-9.31                                                                              w-s.sup.                                               20.2-20.4    4.40-4.35 m                                                      22.0-22.1    4.040-4.022                                                                             m                                                      22.5-22.7    3.952-3.92                                                                              vs                                                     31.6-31.8    2.831-2.814                                                                             w-m                                                    ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined GaAPSO-31 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined GaAPSO-31 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    4                                        O.sub.2  3.46       750      -183    6                                        Cyclohexane                                                                            6.0        90       24      3                                        Neopentane                                                                             6.2        700      24      3                                        H.sub.2 O                                                                              2.65       4.3      24      3                                        H.sub.2 O                                                                              2.65       20       24      10                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of GaAPSO-31 is greater than about 6.2 Å.

EXAMPLE 5 Preparation of GaAPSO-34

A second aliquot of the reaction mixture prepared in Example 1 above wasdigested by sealing it in a stainless steel pressure vessel lined withpolytetrafluoroethylene and heating it in an oven at 200° C. underautogenous pressure for 95 hours. The solid reaction product (which wasdetermined by the analyses described below to be mainly GaAPSO-34) wasrecovered by centrifugation, washed with water and dried in air atambient temperature.

A sample of this solid reaction product was analyzed and the followingchemical analysis obtained:

    ______________________________________                                        Component     Weight percent                                                  ______________________________________                                        Carbon         9.6                                                            Nitrogen       1.2                                                            Ga.sub.2 O.sub.3                                                                            12.9                                                            Al.sub.2 O.sub.3                                                                            26.2                                                            SiO.sub.2     11.3                                                            P.sub.2 O.sub.5                                                                             32.8                                                            LOI*          17.4                                                            ______________________________________                                         *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition inmolar oxide ratios of:

0.39TEAOH:0.27Ga₂ O₃ :1.0Al₂ O₃ :0.73SiO₂ :0.90P₂ O₅ :0.58H₂ O

which corresponds to an empirical chemical formula, on an anhydrousbasis, of:

    0.08TEAOH:(Ga.sub.0.11 Al.sub.0.39 P.sub.0.35 Si.sub.0.14)O.sub.2

so that the product contained gallium, aluminum, silicon and phosphorusin amounts within the pentagonal compositional area defined by points A,B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the major product, assynthesized, was characterized by the data in the following Table LA:

                  TABLE LA                                                        ______________________________________                                        (GaAPSO-34)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         9.5         9.30    100                                                      12.8         6.90    11                                                       14.1         6.29    9                                                        16.0         5.54    37                                                       18.0         4.93    10                                                       20.6         4.32    60                                                       22.2         4.00    2                                                        23.1         3.85    2                                                        25.2         3.53    13                                                       25.8         3.45    13                                                       27.6         3.23    3                                                        28.4         3.15    2                                                        29.5         3.03    3                                                        30.5         2.93    21                                                       31.3         2.861   15                                                       31.6         2.829   4                                                        32.3         2.768   2                                                        33.8         2.649   2                                                        34.4         2.609   6                                                        34.9         2.572   2                                                        36.1         2.490   2                                                        36.3         2.474   3                                                        38.7         2.330   2                                                        39.6         2.274   2                                                        43.1         2.100   2                                                        43.3         2.088   2                                                        47.6         1.912   2                                                        49.0         1.859   5                                                        50.1         1.820   1                                                        51.0         1.791   3                                                        53.1         1.725   2                                                        54.6         1.682   2                                                        ______________________________________                                    

Scanning electron microscopy of the solid product showed numerouscrystals with a morphology corresponding to that expected for GaAPSO-34.Electron microprobe spot analysis of these crystals indicated thefollowing approximate composition:

    Ga.sub.0.06 Al.sub.0.36 P.sub.0.41 Si.sub.0.17

thus indicating that the product contained gallium, aluminum, phosphorusand silicon in amounts within the pentagonal compositional area definedby points A, B, C, D and E of FIG. 1.

EXAMPLE 6 Preparation of GaAPSO-34

An aliquot of a reaction mixture, the preparation of which is describedin Example 10 below, was digested by sealing it in a stainless steelpressure vessel lined with polytetrafluoroethylene and heating it in anoven at 150° C. under autogenous pressure for 72 hours. The solidreaction product (which was determined by the analysis described belowto be mainly GaAPSO-34) was recovered by centrifugation, washed withwater and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major product, assynthesized, was essentially identical to that set forth in Table LAabove.

Scanning electron microscopy of the solid product showed numerouscrystals with a morphology corresponding to that expected for GaAPSO-34.Electron microprobe spot analysis of these crystals indicated thefollowing approximate composition:

    Ga.sub.0.09 Al.sub.0.39 P.sub.0.40 Si.sub.0.11

thus indicating that the product contained gallium, aluminum, phosphorusand silicon in amounts within the pentagonal compositional area definedby points A, B, C, D and E of FIG. 1.

EXAMPLE 7 Preparation of GaAPSO-34

(a) A reaction mixture was formed as described in Example 10 below,except that aluminum isopropoxide was used as the aluminum source. Thecomposition of the final reaction mixture thus produced, expressed interms of the molar oxide ratios of the components of the reactionmixture, was:

1.5TEOH:0.25Ga₂ O₃ :0.75Al₂ O₃ :0.6SiO₂ :0.90P₂ O₅ 0:46H₂ O:4.5i-C₃ H₇OH

This final reaction mixture was digested by sealing it in a stainlesssteel pressure vessel lined with polytetrafluoroethylene and heating itin an oven at 200° C. under autogenous pressure for 354 hours. The solidreaction product (which was determined by the analyses described belowto be mainly GaAPSO-34) was recovered by centrifugation, washed withwater and dried in air at ambient temperature.

The X-ray powder diffraction pattern of the major product, assynthesized, was essentially identical to that set forth in Table LAabove.

A portion of the solid reaction product was calcined in air by heatingto 500° C. at a rate of 100° C. per hour, then holding at 500° C. for 4hours. The calcined product thus produced was impure, but the X-raypowder diffraction pattern of the major product was characterized by thedata in the following Table LB:

                  TABLE LB                                                        ______________________________________                                        (GaAPSO-34)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         9.6         9.17    100                                                      13.1         6.77    21                                                       14.1         6.27    3                                                        16.3         5.45    13                                                       18.0         4.93    8                                                        20.9         4.25    28                                                       22.4         3.97    3                                                        23.4         3.81    4                                                        25.2         3.53    7                                                        26.3         3.39    9                                                        28.1         3.17    5                                                        29.0         3.08    4                                                        30.0         2.980   3                                                        31.1         2.876   16                                                       31.4         2.845   9                                                        34.5         2.602   5                                                        35.0         2.565   5                                                        36.2         2.478   3                                                        ______________________________________                                    

(b) A sample of the calcined product produced in part (a) was utilizedin adsorption capacity studies using a standard McBain-Bakr gravimetricadsorption apparatus. Before being used in the adsorption tests, thesample was activated by heating to 350° C. in a vacuum overnight, andthis activation was repeated before each new adsorbate. The followingdata were generated in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed                                 ______________________________________                                        O.sub.2  3.46       101      -183    16.2                                     O.sub.2  3.46       706      -183    21.3                                     n-Hexane 4.3        60         25.6  7.6                                      iso-Butane                                                                             5.0        700        28.1  0.5                                      H.sub.2 O                                                                              2.65       4.6        27.0  16.8                                     ______________________________________                                    

From the above data, the pore size of the calcined product wasdetermined to be greater than about 4.3 Å, as shown by the adsorption ofn-hexane (kinetic diameter of 4.3 Å), and less than about 5.0 Å as shownby the low adsorption of iso-butane (kinetic diameter of 5.0 Å).

The as-synthesized specimens of GaAPSO-34 prepared in Examples 5, 6 and7, and other as-synthesized specimens of GaAPSO-34 prepared in a similarmanner, all had similar X-ray powder diffraction patterns. The followinggeneral Table LC summarizes the X-ray powder diffraction lines whichwere obtained from the various as-synthesized specimens of GaAPSO-34;the least intense lines were not obtained from every specimen.

                  TABLE LC                                                        ______________________________________                                        (GaAPSO-34)                                                                                          Relative Intensity                                     2θ     d(Å)  100 × I/I.sub.o                                  ______________________________________                                        9.5-9.6      9.4-9.2   100                                                    12.8-12.9    6.93-6.84  8-16                                                  14.1-14.2    6.32-6.24  7-17                                                  15.9-16.1    5.56-5.51 28-49                                                  17.9-18.1    4.94-4.91  9-23                                                  20.5-20.6    4.33-4.31 43-87                                                  22.2-22.4    4.01-3.96  1-10                                                  23.0-23.1    3.86-3.84 2-5                                                    25.2-25.3    3.54-3.52 11-25                                                  25.8-25.9    3.46-3.44 10-19                                                  27.5-27.6    3.24-3.23 3-4                                                    28.3-28.5    3.15-3.13 2-5                                                    29.5-29.6    3.03-3.02 2-4                                                    30.5-30.6    2.933-2.922                                                                             16-29                                                  31.2-31.3    2.868-2.855                                                                             12-22                                                  31.6-31.7    2.834-2.822                                                                             4-5                                                    32.2-32.4    2.778-2.765                                                                             2-3                                                    33.7-33.9    2.656-2.644                                                                             2-3                                                    34.3-34.5    2.613-2.602                                                                              4-12                                                  34.9-35.0    2.572-2.563                                                                             1-8                                                    36.0-36.1    2.493-2.490                                                                             2-3                                                    36.2-36.4    2.480-2.467                                                                             2-7                                                    38.7-38.8    2.330-2.323                                                                             2-3                                                    39.6-39.7    2.276-2.271                                                                             2-4                                                    43.1-43.2    2.100-2.092                                                                             2-4                                                    43.3-43.4    2.088-2.084                                                                             2-4                                                    47.5-47.6    1.916-1.910                                                                             1-4                                                    49.0-49.1    1.860-1.854                                                                             4-7                                                    50.1-50.2    1.821-1.817                                                                             1-2                                                    50.9-51.1    1.793-1.787                                                                             2-4                                                    53.0-53.2    1.727-1.721                                                                             2-5                                                    54.5-54.7    1.682-1.678                                                                             2-3                                                    ______________________________________                                    

EXAMPLE 8 Preparation of GaAPSO-44

(a) GaAPSO-44 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0CHA:0.05-0.2Ga₂ O₃ :0.5-1.0Al₂ O₃ :0.5-1.0P₂ O₅ :0.1-0.6SiO₂:40-100H₂ O

where "CHA" denotes cyclohexylamine.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce GaAPSO-44 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The GaAPSO-44 product's chemical analysis shows the GaAPSO-44 productcontains gallium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a GaAPSO-44 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21   m-vs                                                 15.9-16.3    5.57-5.44 vw-m                                                   20.5-21.0    4.33-4.23   m-vs                                                 24.3-25.1     3.66-3.548                                                                             .sup.  w-m                                             30.5-31.1    2.931-2.876                                                                             vw-m                                                   ______________________________________                                    

(b) When the calcined GaAPSO-44 is utilized in adsorption capacitystudies using a standard McBain-Bakr gravimetric adsorption apparatusthe measurements are Made on a sample after activation at 350° C. in avacuum. The following data are used in the adsorption studies:

    ______________________________________                                                Kinetic    Pressure          Wt. %                                    Adsorbate                                                                             Diameter (Å)                                                                         (Torr)    Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2 3.46       100       -183    13                                       O.sub.2 3.46       750       -183    16                                       n-hexane                                                                              4.3        100         24     2                                       H.sub.2 O                                                                             2.65       4.3         24    15                                       H.sub.2 O                                                                             2.65       20          24    17                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of GaAPSO-44 is about 4.3 Å.

EXAMPLE 9 Preparation of GaAPSO-20

(a) To prepare GaAPSO-20, a reaction mixture was formed by combining 5.2grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with a solution of13.6 grams of tetramethylammonium hydroxide pentahydrate (TMAOH.5H₂ O)in 4.5 grams of water, and adding to the resultant solution a secondsolution prepared by dissolving 4.0 grams of gallium(III) sulfatedodecahydrate (Ga₂ (SO₄)₃.12H₂ O) in 10.0 grams of water. To theresultant mixture were added 3.0 grams of an aqueous silica sol (30 wt.percent SiO₂), followed by 2.5 grams of hydrated aluminum oxide in theform of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃and 24.9 wt. percent H₂ O, and the resultant mixture was stirred untilit was homogeneous. The composition of the final reaction mixture thusproduced, expressed in terms of the molar oxide ratios of the componentsof the reaction mixture, was:

3.0TMAOH:0.25Ga₂ O₃ :0.75Al₂ O₃ :0.6SiO₂ :0.9P₂ O₅ :60H₂ O:0.75H₂ SO₄.

An aliquot of this final reaction mixture was digested by sealing it ina stainless steel pressure vessel lined with polytetrafluoroethylene andheating it in an oven at 150° C. under autogenous pressure for 214hours. The solid reaction product (which was determined by the analysesdescribed below to be GaAPSO-20) was recovered by centrifugation, washedwith water and dried in air at ambient temperature.

A sample of this solid reaction product was analyzed and the followingchemical analysis obtained:

    ______________________________________                                        Component     Weight percent                                                  ______________________________________                                        Carbon        10.5                                                            Nitrogen       2.5                                                            Ga.sub.2 O.sub.3                                                                            11.2                                                            Al.sub.2 O.sub.3                                                                            24.0                                                            SiO.sub.2     10.4                                                            P.sub.2 O.sub.5                                                                             36.1                                                            LOI*          19.7                                                            ______________________________________                                         *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition inmolar oxide ratios of:

0.93TMAOH:0.25Ga₂ O₃ :1.0Al₂ O₃ :0.74SiO₂ :1.08P₂ O₅

which corresponds to an empirical chemical formula, on an anhydrousbasis, of:

    0.17TMAOH:(Ga.sub.0.09 Al.sub.0.37 P.sub.0.40 Si.sub.0.14)O.sub.2

so that the product contained gallium, aluminum, silicon and phosphorusin amounts within the pentagonal compositional area defined by points A,B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the product, as synthesized, wascharacterized by the data in the following Table BA:

                  TABLE BA                                                        ______________________________________                                        (GaAPSO-20)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                        13.9         6.37    45                                                       19.7         4.50    41                                                       22.1         4.02    1                                                        24.2         3.67    100                                                      28.1         3.18    12                                                       31.5         2.844   12                                                       34.5         2.596   18                                                       37.4         2.403   2                                                        40.1         2.249   4                                                        42.7         2.120   3                                                        47.4         1.917   5                                                        51.8         1.764   9                                                        ______________________________________                                    

Scanning electron microscopy of the solid product showed numerouscrystals with a morphology corresponding to that expected for GaAPSO-20.Electron microprobe spot analysis of clean ones of these crystalsindicated the following approximate composition:

    Ga.sub.0.08 Al.sub.0.34 P.sub.0.41 Si.sub.0.17

thus indicating that the product contained gallium, aluminum, phosphorusand silicon in amounts within the pentagonal compositional area definedby points A, B, C, D and E of FIG. 1.

A further aliquot of the reaction mixture was digested in the samemanner as before except that the digestion was conducted at 200° C. for335 hours. The resultant solid reaction product had an X-ray powderdiffraction pattern essentially identical to that set forth in Table BAabove. A portion of this solid reaction product was calcined in air byheating from 100° C. to 500° C. at 100° C. per hour and then heating at500° C. for a further 4 hours. The X-ray powder diffraction pattern ofthe product, as calcined, was characterized by the data in the followingTable BB:

                  TABLE BB                                                        ______________________________________                                        (GaAPSO-20)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                        14.0         6.33    100                                                      19.8         4.48    33                                                       24.3         3.66    86                                                       28.2         3.17    16                                                       31.5         2.837   12                                                       34.7         2.589   14                                                       40.1         2.250   2                                                        42.7         2.118   2                                                        47.5         1.914   2                                                        52.0         1.759   6                                                        ______________________________________                                    

(b) A sample of the calcined product produced in part (a) was utilizedin adsorption capacity studies using a standard McBain-Bakr gravimetricadsorption apparatus. Before being used in the adsorption tests, thesample was activated by heating to 350° C. for 16 hours in vacuum, andthis activation was repeated before each new adsorbate. The followingdata were generated in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed                                 ______________________________________                                        O.sub.2  3.46       706      -183    0.2                                      H.sub.2 O                                                                              2.65       4.6        26.3  6.6                                      ______________________________________                                    

From the above data, the pore size of the calcined product wasdetermined to be greater than about 2.65 Å, as shown by the adsorptionof water (kinetic diameter of 2.65 Å), and less than about 3.46 Å asshown by the low adsorption of oxygen (kinetic diameter of 3.46 Å).X-ray analysis of the material used in these adsorption testsestablished that the X-ray powder diffraction pattern of the materialwas essentially unchanged as a result of contact with the adsorbates.

The specimens of GaAPSO-20 prepared above, and other specimens ofGaAPSO-20 prepared in a similar manner, all had similar X-ray powderdiffraction patterns. The following general Table BC summarizes theX-ray powder diffraction lines which were obtained from the variousspecimens of GaAPSO-20; the least intense lines were not obtained fromevery specimen.

                  TABLE BC                                                        ______________________________________                                        (GaAPSO-20)                                                                                          Relative Intensity                                     2θ     d(Å)  100 × I/I.sub.o                                  ______________________________________                                        13.9-14.0    6.37-6.34 45-47                                                  19.7-19.8    4.50-4.48 41-43                                                  22.1-22.2    4.02-4.01 1-2                                                    24.2-24.3    3.67-3.66 100                                                    28.1         3.18-3.17 12                                                     31.5         2.844-2.838                                                                             12                                                     34.5-34.6    2.596-2.591                                                                             18-20                                                  37.4-37.5    2.403-2.398                                                                             2-3                                                    40.1-40.2    2.249-2.245                                                                             4                                                      42.7         2.120-2.116                                                                             3-4                                                    47.4-47.5    1.917-1.914                                                                             5                                                      51.8-51.9    1.764-1.761                                                                             9                                                      ______________________________________                                    

EXAMPLE 10 Preparation of GaAPSO-26

To prepare GaAPSO-26, a solution was formed by combining 6.9 grams of 85wt. percent orthophosphoric acid (H₃ PO₄) with 12.5 grams of water. Thissolution was combined with 3.4 grams of hydrated aluminum oxide in theform of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃and 24.9 wt. percent of H₂ O. To the resultant mixture were added 4.0grams of an aqueous silica sol (30 wt. percent SiO₂), and to theresultant mixture was added a solution prepared by dissolving 1.8 gramsof gallium(III) hydroxide (86.4 wt. percent Ga₂ O₃) in 18.4 grams of 40wt. percent aqueous tetraethylammonium hydroxide (TEAOH), and theresultant mixture was stirred until it was homogeneous. The compositionof the final reaction mixture thus produced, expressed in terms of themolar oxide ratios of the components of the reaction mixture, was:

1.5TEAOH:0.25Ga₂ O₃ :0.75Al₂ O₃ :0.6SiO₂ :0.9P₂ O₅ :50H₂ O.

This final reaction mixture was digested by sealing it in a stainlesssteel pressure vessel lined with polytetrafluoroethylene and heating itin an oven at 150° C. under autogenous pressure for 72 hours. The solidreaction product (which was determined by the analyses described belowto be a mixture of two crystalline components, one of which wasGaAPSO-26) was recovered by centrifugation, washed with water and driedin air at ambient temperature.

The X-ray powder diffraction pattern of the GaAPSO-26 product, assynthesized, was characterized by the data in the following Table XA:

                  TABLE XA                                                        ______________________________________                                        (GaAPSO-26)                                                                                       Relative Intensity                                        2θ    d(Å)                                                                              100 × I/I.sub.o                                     ______________________________________                                         8.2        10.7    100                                                        9.6        9.25    *                                                         10.5        8.45    3                                                         14.2        6.25    *                                                         15.2        5.84    12                                                        17.3        5.13    6                                                         17.7        5.00    8                                                         19.5        4.54    5                                                         21.8        4.07    11                                                        22.4        3.96    16                                                        24.2        3.67    2                                                         24.8        3.59    4                                                         27.0        3.31    6                                                         27.6        3.23    2                                                         28.5        3.13    4                                                         29.2        3.06    3                                                         29.9        2.99    3                                                         30.4        2.94    *                                                         31.2        2.87    *                                                         31.7        2.822   7                                                         33.7        2.663   5                                                         34.4        2.606   3                                                         34.9        2.571   1                                                         36.4        2.467   4                                                         38.2        2.355   3                                                         47.5        1.912   3                                                         ______________________________________                                         *denotes minor peak masked by peak from the other crystalline component. 

Scanning electron microscopy of the solid product showed numerouscrystals with a morphology corresponding to that expected for GaAPSO-26.Electron microprobe spot analysis of clean ones of these crystalsindicated the following approximate composition:

    Ga.sub.0.19 Al.sub.0.24 P.sub.0.49 Si.sub.0.08

thus indicating that the product contained gallium, aluminum, phosphorusand silicon in amounts within the pentagonal compositional area definedby points A, B, C, D and E of FIG. 1.

Other specimens of GaAPSO-26 prepared in a similar manner had similarX-ray powder diffraction patterns. The following general Table XBsummarizes the X-ray powder diffraction lines which were obtained fromthe various specimens of GaAPSO-26; the least intense lines were notobtained from every specimen.

                  TABLE XB                                                        ______________________________________                                        (GaAPSO-26)                                                                                         Relative Intensity                                      2θ    d(Å)  100 × I/I.sub.o                                   ______________________________________                                         8.2        10.8-10.7 100                                                     9.5-9.6     9.28-9.25 *                                                       10.5-10.6   8.45-8.42  3-13                                                   14.1-14.2   6.27-6.24 *                                                       15.2        5.84      12-19                                                   17.3        5.13-5.12  6-11                                                   17.7-17.8   5.00-4.99  8-14                                                   19.5        4.55-4.54  5-11                                                   21.8        4.07      10-18                                                   22.4        3.97-3.96 16-24                                                   24.2        3.67      2-5                                                     24.8-24.9   3.59-3.57 4-8                                                     27.0        3.31-3.30  6-12                                                   27.6        3.23      1-2                                                     28.5-28.7   3.14-3.11 4-7                                                     29.2        3.06      3                                                       29.9        2.99      3                                                       30.4        2.94      *                                                       31.2-31.3   2.87-2.86 *                                                       31.7        2.824-2.822                                                                             7                                                       33.7         2.663    5                                                       34.4        2.607-2.606                                                                             3                                                       34.9        2.571-2.569                                                                             1                                                       36.4        2.471-2.467                                                                             1-4                                                     38.2        2.358-2.355                                                                             1-3                                                     47.5        1.914-1.912                                                                             1-3                                                     ______________________________________                                         *denotes minor peak often masked by peak from the other crystalline           component.                                                               

EXAMPLE 11 Preparation of GaAPSO-35

(a) To prepare GaAPSO-35, a solution was formed by dissolving 3.6 gramsof gallium(III) sulfate dodecahydrate (Ga₂ (SO₄)₃.12H₂ O) in 8.0 gramsof water, and combining the resultant solution with 2.3 grams ofhydrated aluminum oxide in the form of a pseudo-boehmite phasecomprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent of H₂ O. Tothe resultant mixture were added 2.7 grams of an aqueous silica sol (30wt. percent SiO₂). A second mixture was prepared by dissolving 7.4 gramsof quinuclidine (QN) in 10.9 grams of water and adding the resultantsolution to 4.6 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄).The two mixtures were combined and the resultant mixture was stirreduntil it was homogeneous. The composition of the final reaction mixturethus produced, expressed in terms of the molar oxide ratios of thecomponents of the reaction mixture, was:

3.0QN:0.25Ga₂ O_(3:) 0.75Al₂ O₃ :0.6SiO₂ :0.9P₂ O₅ :60H₂ O:0.75H₂ SO₄.

An aliquot of this final reaction mixture was digested by sealing it ina stainless steel pressure vessel lined with polytetrafluoroethylene andheating it in an oven at 150° C. under autogenous pressure for 336hours. The solid reaction product (which was determined by the analysesdescribed below to be substantially pure GaAPSO-35) was recovered bycentrifugation, washed with water and dried in air at ambienttemperature.

A sample of this solid reaction product was analyzed and the followingchemical analysis obtained:

    ______________________________________                                        Component     Weight percent                                                  ______________________________________                                        Carbon        11.3                                                            Nitrogen       1.6                                                            Ga.sub.2 O.sub.3                                                                             4.5                                                            Al.sub.2 O.sub.3                                                                            27.0                                                            SiO.sub.2     17.5                                                            P.sub.2 O.sub.5                                                                             29.3                                                            LOI*          20.0                                                            ______________________________________                                         *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition inmolar oxide ratios of :

0.51QN:0.09Ga₂ O₃ :1.0Al₂ O₃ :1.10SiO₂ :0.78P₂ O₅ :1.06H₂ O

which corresponds to an empirical chemical formula, on an anhydrousbasis, of:

    0.11QN:(Ga.sub.0.04 Al.sub.0.41 P.sub.0.32 Si.sub.0.23)O.sub.2

so that the product contained gallium, aluminum, silicon and phosphorusin amounts within the pentagonal compositional area defined by points A,B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the product, as synthesized, wascharacterized by the data in the following Table MA:

                  TABLE MA                                                        ______________________________________                                        (GaAPSO-35)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         8.7         10.21   20                                                       11.0         8.03    49                                                       11.8         7.48    3                                                        13.4         6.63    30                                                       15.9         5.57    9                                                        17.3         5.11    70                                                       17.9         4.96    17                                                       20.8         4.26    15                                                       21.2         4.19    55                                                       21.9         4.05    100                                                      23.2         3.83    18                                                       23.7         3.75    8                                                        25.1         3.54    5                                                        26.9         3.32    20                                                       27.4         3.26    2                                                        28.6         3.12    23                                                       28.8         3.10    23                                                       31.3         2.857   2                                                        32.1         2.787   46                                                       34.7         2.584   9                                                        35.0         2.563   3                                                        35.7         2.512   5                                                        37.8         2.383   2                                                        39.3         2.290   3                                                        42.2         2.141   5                                                        42.5         2.128   4                                                        43.2         2.094   4                                                        44.5         2.034   2                                                        48.6         1.873   9                                                        49.5         1.843   6                                                        51.6         1.772   7                                                        55.3         1.661   6                                                        ______________________________________                                    

Scanning electron microscopy of the solid product showed numerouscrystals with a morphology corresponding to that expected for GaAPSO-35.Electron microprobe spot analysis of clean ones of these crystalsindicated the following approximate composition:

    Ga.sub.0.05 Al.sub.0.35 P.sub.0.32 Si.sub.0.29

thus indicating that the product contained gallium, aluminum, phosphorusand silicon in amounts within the pentagonal compositional area definedby points A, B, C, D and E of FIG. 1.

A further aliquot of the reaction mixture was digested in the samemanner as before except that the digestion was conducted at 200° C. for672 hours. The resultant solid reaction product had an X-ray powderdiffraction pattern essentially identical to that set forth in Table MAabove. A portion of this solid reaction product was calcined in air byheating from 100° C. to 500° C. at 100° C. per hour and then heating at500° C. for a further 2 hours. The X-ray powder diffraction pattern ofthe product, as calcined, was characterized by the data in the followingTable MB:

                  TABLE MB                                                        ______________________________________                                        (GaAPSO-35)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         8.5         10.4    8                                                         8.7         10.1    22                                                       11.0         8.02    100                                                      13.0         6.81    5                                                        13.5         6.54    81                                                       16.1         5.51    5                                                        17.5         5.08    35                                                       21.0         4.22    35                                                       21.6         4.11    5                                                        22.2         4.01    72                                                       23.0         3.86    5                                                        23.5         3.78    19                                                       25.1         3.55    15                                                       26.0         3.427   7                                                        26.6         3.352   4                                                        27.2         3.274   20                                                       28.6         3.125   43                                                       29.5         3.03    11                                                       31.7         2.827   5                                                        32.5         2.752   32                                                       34.6         2.593   8                                                        35.3         2.539   5                                                        36.3         2.476   4                                                        42.2         2.142   4                                                        43.1         2.101   5                                                        50.2         1.819   4                                                        51.8         1.765   4                                                        ______________________________________                                    

(b) A sample of the calcined product produced in part (a) was utilizedin adsorption capacity studies using a standard McBain-Bakr gravimetricadsorption apparatus. Before being used in the adsorption tests, thesample was activated by heating to 350° C. for 16 hours in vacuum, andthis activation was repeated before each new adsorbate. The followingdata were generated in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed                                 ______________________________________                                        O.sub.2  3.46       101      -183    14.2                                     O.sub.2  3.46       706      -183    17.9                                     n-Hexane 4.3        60         25.6  6.8                                      iso-Butane                                                                             5.0        700        28.1  0.7                                      H.sub.2 O                                                                              2.65       4.6        27.0  11.4                                     ______________________________________                                    

From the above data, the pore size of the calcined product wasdetermined to be greater than about 4.3 Å, as shown by the adsorption ofn-hexane (kinetic diameter of 4.3 Å), and less than about 5.0 Å as shownby the low adsorption of iso-butane (kinetic diameter of 5.0 Å). X-rayanalysis of the material used in these adsorption tests established thatthe X-ray powder diffraction pattern of the material was essentiallyunchanged as a result of contact with the adsorbates.

Other specimens of GaAPSO-35 prepared in a similar manner had similarX-ray powder diffraction patterns. The following general Table MCsummarizes the X-ray powder diffraction lines which were obtained fromthe various specimens of GaAPSO-35; the least intense lines were notobtained from every specimen.

                  TABLE MC                                                        ______________________________________                                        (GaAPSO-35)                                                                                         Relative Intensity                                      2θ    d(Å)  100 × I/I.sub.o                                   ______________________________________                                         8.5        10.4      8                                                        8.7        10.2      20-25                                                   11.0        8.03-8.02  49-100                                                 11.8        7.50-7.48 3-7                                                     13.0        6.81      5                                                       13.4-13.5   6.63-6.54 30-81                                                   15.9-16.1   5.57-5.51  5-10                                                   17.3-17.5   5.12-5.08 35-71                                                   17.9        4.97-4.96 15-16                                                   20.8        4.27-4.26 15                                                      21.0-21.6   4.22-4.11 35-63                                                   21.9-22.2   4.06-4.01  72-100                                                 23.0-23.2   3.86-3.83  5-18                                                   23.5-23.7   3.78-3.75  8-19                                                   25.1        3.54       5-15                                                   26.0-26.6   3.43-3.35 4-7                                                     26.8-27.2   3.32-3.27 20-21                                                   27.3-27.4   3.27-3.26 2-3                                                     28.5-28.8   3.13-3.10 23-43                                                   29.5        3.03      11                                                      31.3-31.7   2.857-2.827                                                                             2-5                                                     32.1-32.5   2.787-2.752                                                                             32-47                                                   34.6-34.7   2.593-2.584                                                                              8-12                                                   35.3-35.7   2.539-2.512                                                                             5-6                                                     37.7-37.8   2.387-2.383                                                                             2                                                       39.3        2.292-2.290                                                                             3-4                                                     42.1-42.2   2.145-2.141                                                                             4-5                                                     42.4-42.5   2.131-2.128                                                                             4-5                                                     43.1-43.2   2.098-2.094                                                                             4-5                                                     44.5         2.034    2                                                       48.6        1.875-1.873                                                                              9-10                                                   49.4-50.2   1.844-1.819                                                                             4-6                                                     51.5-51.8   1.755-1.765                                                                             4-7                                                     55.2-55.3   1.663-1.661                                                                             6                                                       ______________________________________                                    

PROCESS APPLICATIONS

The GaAPSO compositions of the present invention are, in general,hydrophilic and adsorb water preferentially over common hydrocarbonmolecules such as paraffins, olefins and aromatic species, e.g.,benzene, xylenes and cumene. Thus the present molecular sievecompositions as a class are useful as desiccants in such adsorptionseparation/purification processes as natural gas drying, cracked gasdrying. Water is also preferentially adsorbed over the so-calledpermanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen.These GaAPSOs are therefore suitably employed in the drying of reformerhydrogen streams and in the drying of oxygen, nitrogen or air prior toliquifaction.

The present GaAPSO compositions also exhibit novel surface selectivitycharacteristics which render them useful as catalyst or catalyst basesin a number of hydrocarbon conversion and oxidative combustionreactions. They can be impregnated or otherwise loaded withcatalytically active metals by methods well known in the art (forexample ion exchange) and used, for example, in fabricating catalystcompositions having silica or alumina bases. Of the general class, thosespecies having pores larger than about 4A are preferred for catalyticapplications.

Among the hydrocarbon conversion reactions catalyzed by GaAPSOcompositions are cracking, hydrocracking, alkylation for both thearomatic and isoparaffin types, isomerization including xyleneisomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydrodecyclization anddehydrocyclization.

Using GaAPSO catalyst compositions which contain a hydrogenationpromoter such as platinum or palladium, heavy petroleum residual stocks,cyclic stocks and other hydrocrackable charge stocks, can behydrocracked at temperatures in the range of 400° F. to 825° F. (204° C.to 411° C.) using molar ratios of hydrogen to hydrocarbon in the rangeof between 2 and 80, pressures between 10 and 3500 p.s.i.g. (0.171 to24.23 MPa.), and a liquid hourly space velocity (LHSV) of from 0.1 to20, preferably 1.0 to 10.

The GaAPSO catalyst compositions employed in hydrocracking are alsosuitable for use in reforming processes in which the hydrocarbonfeedstocks contact the catalyst at temperatures of from about 700° F. to1000° F. (371° C. to 538° C.), hydrogen pressures of from 100 to 500p.s.i.g. (0.791 to 3.448 MPa.), LHSV values in the range of 0.1 to 10and hydrogen to hydrocarbon molar ratios in the range of 1 to 20,preferably between 4 and 12.

These same catalysts, i.e. those containing hydrogenation promoters, arealso useful in hydroisomerization processes in which feedstocks such asnormal paraffins are converted to saturated branched chain isomers.Hydroisomerization is carried out at a temperature of from about 200° F.to 600° F. (93° C. to 316° C.), preferably 300° F. to 550° F. (149° C.to 288° C.) with an LHSV value of from about 0.2 to 1.0. Hydrogen (H) issupplied to the reactor in admixture with the hydrocarbon (Hc) feedstockin molar proportions (H/Hc) of between 1 and 5.

At somewhat higher temperatures, i.e. from about 650° F. to 1000° F.(343° C. to 538° C.), preferably 850° F. to 950° F. (454° C. to 510° C.)and usually at somewhat lower pressures within the range of about 15 to50 p.s.i.g. (205 to 446 KPa.), the same catalyst compositions are usedto hydroisomerize normal paraffins. Preferably the paraffin feedstockcomprises normal paraffins having a carbon number range of C₇ -C₂₀.Contact time between the feedstock and the catalyst is generallyrelatively short to avoid undesirable side reactions such as olefinpolymerization and paraffin cracking. LHSV values in the range of 0.1 to10, preferably 1.0 to 6.0 are suitable.

The unique crystal structure of the present GaAPSO catalysts and theiravailability in a form totally void of alkali metal content favor theiruse in the conversion of alkylaromatic compounds, particularly thecatalytic disproportionation to toluene, ethylene, trimethyl benzenes,tetramethyl benzenes and the like. In the disproportionation process,isomerization and transalkylation can also occur. Group VIII noble metaladjuvants alone or in conjunction with Group VI-B metals such astungsten, molybdenum and chromium are preferably included in thecatalyst composition in amounts of from about 3 to 15 weight-% of theoverall composition. Extraneous hydrogen can, but need not, be presentin the reaction zone which is maintained at a temperature of from about400° to 750° F. (204° to 399° C.), pressures in the range of 100 to 2000p.s.i.g. (0.791 to 13.89 MPa.) and LHSV values in the range of 0.1 to15.

Catalytic cracking processes are preferably carried out with GaAPSocompositions using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc., with gasoline being the principaldesired product. Temperature conditions of 850° to 1100° F. (454° to593° C.), LHSV values of 0.5 to 10 and pressure conditions of from about0 to 50 p.s.i.g. (101 to 446 KPa.) are suitable.

Dehydrocyclization reactions employing paraffinic hydrocarbonfeedstocks, preferably normal paraffins having more than 6 carbon atoms,to form benzene, xylenes, toluene and the like are carried out usingessentially the same reaction conditions as for catalytic cracking. Forthese reactions it is preferred to use the GaAPSO catalyst inconjunction with a Group VIII non-noble metal cation such as cobalt andnickel. In catalytic dealkylation wherein it is desired to cleaveparaffinic side chains from aromatic nuclei without substantiallyhydrogenating the ring structure, relatively high temperatures in therange of about 800°-1000° F. (427°-538° C.) are employed at moderatehydrogen pressures of about 300-1000 p.s.i.g. (2.17-6.895 MPa.), otherconditions being similar to those described above for catalytichydrocracking. Preferred catalysts are of the same type described abovein connection with catalytic dehydrocyclization. Particularly desirabledealkylation reactions contemplated herein include the conversion ofmethylnaphthalene to naphthalene and toluene and/or xylenes to benzene.

In catalytic hydrofining, the primary objective is to promote theselective hydrodecomposition of organic sulfur and/or nitrogen compoundsin the feed, without substantially affecting hydrocarbon moleculestherein. For this purpose it is preferred to employ the same generalconditions described above for catalytic hydrocracking, and catalysts ofthe same general nature described in connection with dehydrocyclizationoperations. Feedstocks include gasoline fractions, kerosenes, jet fuelfractions, diesel fractions, light and heavy gas oils, deasphalted crudeoil residua and the like. Any of these may contain up to about 5weight-percent of sulfur and up to about 3 weight-percent of nitrogen.

Similar conditions can be employed to effect hydrofining, i.e.,denitrogenation and desulfurization, of hydrocarbon feeds containingsubstantial proportions of organonitrogen and organosulfur compounds. Itis generally recognized that the presence of substantial amounts of suchconstituents markedly inhibits the activity of hydrocracking catalysts.Consequently, it is necessary to operate at more extreme conditions whenit is desired to obtain the same degree of hydrocracking conversion perpass on a relatively nitrogenous feed than with a feed containing lessorganonitrogen compounds. Consequently, the conditions under whichdenitrogenation, desulfurization and/or hydrocracking can be mostexpeditiously accomplished in any given situation are necessarilydetermined in view of the characteristics of the feedstocks, inparticular the concentration of organonitrogen compounds in thefeedstock. As a result of the effect of organonitrogen compounds on thehydrocracking activity of these compositions it is not at all unlikelythat the conditions most suitable for denitrogenation of a givenfeedstock having a relatively high organonitrogen content with minimalhydrocracking, e.g., less than 20 volume percent of fresh feed per pass,might be the same as those preferred for hydrocracking another feedstockhaving a lower concentration of hydrocracking inhibiting constituentse.g., organonitrogen compounds. Consequently, it has become the practicein this art to establish the conditions under which a certain feed is tobe contacted on the basis of preliminary screening tests with thespecific catalyst and feedstock.

Isomerization reactions are carried out under conditions similar tothose described above for reforming, using somewhat more acidiccatalysts. Olefins are preferably isomerized at temperatures of500°-900° F. (260°-482° C.), while paraffins, naphthenes and alkylaromatics are isomerized at temperatures of 700°-1000° F. (371°-538°C.). Particularly desirable isomerization reactions contemplated hereininclude the conversion of n-heptane and/or n-octane to isoheptanes,iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane,meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-buteneand/or isobutene, n-hexane to isohexene, cyclohexene tomethylcyclopentene etc. The preferred form of the catalyst is acombination of the GaAPSO with polyvalent metal compounds (such assulfides) of metals of Group II-A, Group II-B and rare earth metals. Foralkylation and dealkylation processes the GaAPSO compositions havingpores of at least 5 Å are preferred. When employed for dealkylation ofalkyl aromatics, the temperature is usually at least 350° F. (177° C.)and ranges up to a temperature at which substantial cracking of thefeedstock or conversion products occurs, generally up to about 700° F.(371° C.). The temperature is preferably at least 450° F. (232° C.) andnot greater than the critical temperature of the compound undergoingdealkylation. Pressure conditions are applied to retain at least thearomatic feed in the liquid state. For alkylation the temperature can beas low as 250° F. (121° C.) but is preferably at least 350° F. (177° C).In the alkylation of benzene, toluene and xylene, the preferredalkylating agents are olefins such as ethylene and propylene.

The following examples are provided to further illustrate the use of theGaAPSOs of the invention in one of the processes discussed above, butare not intended to be limitative of the possible uses of the GaAPSOs.

EXAMPLE 12 Cracking Tests on GaAPSO-34

The n-butane cracking activity of the calcined GaAPSO-34 prepared inExample 7 above was tested in a bench-scale apparatus, in which thereactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. ininternal diameter. This reactor was loaded with the calcined GaAPSO-34,which was in the form of particles having sizes of 20-40 U.S. mesh. Themixture was then activated in situ by heating from ambient temperatureto 500° C. under helium, and then holding the sample at 500° C. in airfor 1 hour; the weight of the activated mixture in the reactor was 0.82grams.

A feedstock comprising a helium/n-butane mixture containing 2 molepercent of n-butane was then passed through the reactor at a rate of 50mL/min. The reactor effluent was analyzed after 10 minutes of on-streamoperation using conventional gas chromatography techniques. Theresultant data showed a pseudo-first-order rate constant (k_(A)) of10.0.

EXAMPLE 13 Cracking Tests on GaAPSO-20

The n-butane cracking activity of the calcined GaAPSO-20 prepared inExample 9 above was tested in the same way as in Example 12 above,except that the weight of the activated mixture in the reactor was 0.62gram. The resultant data showed a pseudo-first-order rate constant of0.5.

What is claimed is:
 1. Crystalline molecular sieves havingthree-dimensional microporous framework structures of GaO₂, AlO₂, PO₂and SiO₂ tetrahedral units having an empirical chemical composition onan anhydrous basis expressed by the formula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of gallium, aluminum, phosphorus and silicon respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D, and E of FIG. 1, said crystalline molecular sieves having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in one of the following Tables A to H and J toX:

                  TABLE A                                                         ______________________________________                                        (GaAPSO-5)                                                                    2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-7.7      12.28-11.48                                                                             m-vs                                                   19.4-19.9    4.58-4.46 w-m                                                    20.85-21.3   4.26-4.17 w-vs                                                   22.1-22.6    4.02-3.93 m-vs                                                   25.6-26.2    3.480-3.402                                                                             vw-m                                                   ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        (GaAPSO-11)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.8-8.2      11.19-10.85                                                                             m-s .sup.                                              9.0-9.8      9.83-9.03 vw-vs .sup.                                            12.8-13.6    6.92-6.51 vw-m                                                   19.9-20.5    4.46-4.33 m-s .sup.                                              20.8-21.8    4.27-4.08 m-vs                                                   22.0-22.6    4.04-3.93 m-vs                                                   22.6-23.1    3.93-3.85 vw-vs .sup.                                            23.1-23.5    3.85-3.79 w-vs                                                   ______________________________________                                    

                  TABLE C                                                         ______________________________________                                        (GaAPSO-14)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                         8.6-8.9     10.3-9.93                                                                              vs                                                      13.0         6.81     w                                                       21.9-22.2    4.06-4.00                                                                              w                                                       25.4         3.51     w                                                       27.5         3.24     w                                                       29.7         3.01     w                                                       ______________________________________                                    

                  TABLE D                                                         ______________________________________                                        (GaAPSO-16)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        11.3-11.6    7.83-7.63  w-vs                                                  18.55-18.9   4.78-4.70 vw-m .sup.                                             21.85-22.2   4.07-4.00  m-vs                                                  22.8-23.3    3.900-3.818                                                                             w-m                                                    26.4-27.3    3.370-3.267                                                                             w-m                                                    29.6-29.9    3.018-2.988                                                                             w-m                                                    ______________________________________                                    

                  TABLE E                                                         ______________________________________                                        (GaAPSO-17)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.70-7.75    11.5-11.4 vs                                                     13.4         6.61       s-vs                                                   15.5-15.55  5.72-5.70 s                                                      19.65-19.7   4.52-4.51 w-s                                                    20.5-20.6    4.33-4.31 vs                                                     31.8-32.0    2.812-2.797                                                                             w-s                                                    ______________________________________                                    

                  TABLE F                                                         ______________________________________                                        (GaAPSO-18)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                         9.6-9.65    9.21-9.16 vs                                                      15.5-15.55  5.72-5.70 m                                                      16.9-17.1    5.25-5.19 m                                                      20.15-20.25  4.41-4.39 m                                                      20.95-21.05  4.24-4.22 m                                                      31.8-32.5    2.814-2.755                                                                             m                                                      ______________________________________                                    

                  TABLE G                                                         ______________________________________                                        (GaASPO-20)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.8-14.2    6.42-6.23 m-vs                                                    19.6-20.15  6.53-4.41 m                                                      24.1-24.8    3.695-3.603                                                                             m-vs                                                   27.9-28.6    3.198-3.121                                                                             w                                                      31.3-32.1    2.861-2.791                                                                             w                                                      34.35-35.0   2.610-2.601                                                                             w-m                                                    ______________________________________                                    

                  TABLE H                                                         ______________________________________                                        (GaAPSO-31)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.4-9.5      10.53-9.31                                                                              w-s                                                    20.2-20.4    4.40-4.35 m                                                      22.0-22.1    4.040-4.022                                                                             m                                                      22.5-22.7    3.952-3.92                                                                              vs                                                     31.6-31.8    2.831-2.814                                                                             w-m                                                    ______________________________________                                    

                  TABLE J*                                                        ______________________________________                                        (GaAPSO-33)                                                                   2θ      d(Å) Relative Intensity                                     ______________________________________                                        9.25-9.55     9.56-9.26                                                                              w-m                                                    12.5-12.9     7.08-6.86                                                                              vs                                                     16.9-17.3     5.25-5.13                                                                              w-m                                                    20.45-20.9    4.34-4.25                                                                              w-m                                                    23.85-24.25   3.73-3.67                                                                              w-m                                                    26.05-26.35   3.42-3.38                                                                              w-m                                                    27.3-27.6     3.27-3.23                                                                              vs                                                     ______________________________________                                         *as-synthesized form                                                     

                  TABLE K*                                                        ______________________________________                                         (GaAPSO-33)                                                                  2θ      d(Å) Relative Intensity                                     ______________________________________                                        13.15-13.4    6.73-6.61                                                                              vs                                                     18.05-18.35   4.91-4.83                                                                              m                                                      18.4-18.6     4.82-4.77                                                                              m                                                      26.55-26.7    3.36-3.34                                                                              m                                                      32.0-32.1     2.80-2.79                                                                              m                                                      ______________________________________                                         *calcined form                                                           

                  TABLE L                                                         ______________________________________                                        (GaAPSO-34)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.3-9.8      9.51-9.03   m-vs                                                 12.6-13.2    7.03-6.71  .sup. w-m                                             15.8-16.3    5.61-5.44 vw-m                                                   20.25-21.2   4.39-4.19   w-vs                                                 24.8-25.4     3.59-3.507                                                                             vw-m                                                   30.0-30.9    2.979-2.894                                                                             vw-m                                                   ______________________________________                                    

                  TABLE M                                                         ______________________________________                                        (GaAPSO-35)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        10.6-11.1    8.35-7.97 vw-vs                                                  13.1-13.7    6.76-6.46 vw-vs                                                  17.0-17.6    5.22-5.04 w-s                                                    20.6-21.6    4.31-4.11 vw-m                                                   21.6-22.3    4.11-3.99 .sup.  m-vs                                            28.1-28.8    3.175-3.100                                                                             vw-m                                                   ______________________________________                                    

                  TABLE N                                                         ______________________________________                                        (GaAPSO-36)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.45-8.0     11.14-11.05                                                                             vs                                                     8.1-8.3      10.91-10.65                                                                             w-m                                                    16.3-16.6    5.44-5.34 w-m                                                    18.9-19.4    4.70-4.57 w-m                                                    20.7-21.0    4.29-4.23 w-m                                                    ______________________________________                                    

                  TABLE O                                                         ______________________________________                                        (GaAPSO-37)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        6.1-6.3      14.49-14.03                                                                             vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE P                                                         ______________________________________                                        (GaAPSO-39)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m                                                      13.1-13.5    6.76-6.56 m                                                      17.8-18.4    4.98-4.82 w-m                                                    20.8-21.3    4.27-4.17  m-vs                                                   22.2-22.85   4.00-3.892                                                                              m-vs                                                   26.4-27.05  3.376-3.296                                                                             w-m                                                    ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (GaAPSO-40)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.5-7.7      11.79-11.48                                                                             vw-m .sup.                                             8.0-8.1      11.05-10.94                                                                             .sup.  s-vs                                            12.4-12.5    7.14-7.08  w-vs                                                  13.6-13.8    6.51-6.42 m-s                                                    14.0-14.1    6.33-6.28 w-m                                                    27.8-28.0    3.209-3.187                                                                             w-m                                                    ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (GaAPSO-41)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.6-13.8    6.51-6.42 w-m                                                    20.5-2.6     4.33-4.31 w-m                                                    21.1-21.3    4.21-4.17 vs                                                     22.1-22.3    4.02-3.99 m-s                                                    22.8-23.0    3.90-3.86 m                                                      23.1-23.4    3.82-3.80 w-m                                                    25.5-25.9    3.493-3.44                                                                              w-m                                                    ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (GaAPSO-42)                                                                   2θ      d(Å)  Relative Intensity                                    ______________________________________                                        7.15-7.4      12.36-11.95                                                                              .sup. m-vs                                            12.5-12.7    7.08-6.97 m-s                                                   21.75-21.9    4.09-4.06 m-s                                                    24.1-24.25   3.69-3.67 vs                                                    27.25-27.4    3.273-3.255                                                                             s                                                      30.05-30.25  2.974-2.955                                                                             m-s                                                   ______________________________________                                    

                  TABLE T                                                         ______________________________________                                        (GaAPSO-43)                                                                   2θ      d(Å)  Relative Intensity                                    ______________________________________                                        12.3-12.95    7.20-6.83 m-vs                                                  16.8-17.45    5.28-5.09 vw-w                                                  21.45-21.85   4.145-4.071                                                                             m-vs                                                  27.1-27.85    3.291-3.232                                                                             w-vs                                                  32.4-33.2     2.763-2.699                                                                             vw-m                                                  ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (GaAPSO-44)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m-vs                                                   15.9-16.3    5.57-5.44 vw-m                                                   20.5-21.0    4.33-4.23 m-vs                                                   24.3-25.1     3.66-3.548                                                                             w-m                                                    30.5-31.1    2.931-2.876                                                                             vw-m                                                   ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        (GaAPSO-46)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-8.1      12.28-10.92                                                                             vs                                                     12.9-13.6    6.86-6.51 vw                                                     21.2-22.2     4.19-4.501                                                                             vw-m                                                    22.5-23.45   3.95-3.793                                                                             vw-m                                                   26.6-27.9    3.351-3.198                                                                             vw-m                                                   ______________________________________                                    

                  TABLE W                                                         ______________________________________                                        (GaAPSO-47)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.4-9.6      9.41-9.21 vs                                                     12.8-13.1    6.92-6.76 vw-m                                                   16.0-16.3    5.54-5.44 vw-m                                                   20.5-21.0    4.31-4.23   m-vs                                                 24.6-25.3    3.613-3.526                                                                             vw-m                                                   30.6-31.1    2.921-2.876                                                                             vw-m                                                   ______________________________________                                    

                  TABLE X                                                         ______________________________________                                        (GaAPSO-26)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                         8.2         10.8-10.7                                                                              vs                                                      10.5-10.6    8.45-8.42                                                                              vw-w                                                    15.2         5.84     w                                                       17.7--17.8   5.00-4.99                                                                              vw-w                                                    21.8         4.07     w                                                       22.4         3.97-3.96                                                                                w-m.                                                  ______________________________________                                    


2. Crystalline molecular sieves according to claim 1 wherein the molefractions of gallium, aluminum, phosphorus and silicon present astetrahedral oxides are within the hexagonal compositional area definedby points a, b, c, d, e and f of FIG.
 2. 3. Crystalline molecular sievesaccording to claim 2 wherein the mole fractions of gallium, aluminum,phosphorus and silicon present as tetrahedral oxides are within thehexagonal compositional area defined by points g, h, i, j, k and l ofFIG.
 2. 4. The crystalline molecular sieves according to claim 1 orclaim 2 wherein "m" is not greater than about 0.2.
 5. The crystallinemolecular sieves of claim 1 or 2 having a characteristic X-ray powderdiffraction pattern which contains at least the d-spacings set forth inTable A given in claim
 1. 6. The crystalline molecular seives of claim 5wherein the X-ray powder diffraction pattern set forth in Table Acontains at least the d-spacings set forth in the following Table AA:

                  TABLE AA                                                        ______________________________________                                        (GaAPSO-5)                                                                                         Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         7.5         11.8    100                                                      12.9         6.84    10                                                       13.0         6.81    10                                                       19.9         4.45    44                                                       21.3         4.17    34                                                       22.6         3.93    61                                                       24.8         3.60     3                                                       26.2         3.41    22                                                       29.3         3.05    11                                                       30.3          2.947  18                                                       33.9          2.645   6                                                       34.5          2.599   6                                                       34.8          2.577  12                                                       38.1          2.362   
 7.                                                     ______________________________________                                    


7. The crystalline molecular sieves of claim 1 or 2 having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in Table B given in claim
 1. 8. The crystallinemolecular sieves of claim 7 wherein the X-ray powder diffraction patternset forth in Table B contains at least the d-spacings set forth in oneof the following Tables BA and BB:

                  TABLE BA                                                        ______________________________________                                        (GaAPSO-20)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                        13.9         6.37    45                                                       19.7         4.50    41                                                       22.1         4.02    1                                                        24.2         3.67    100                                                      28.1         3.18    12                                                       31.5         2.844   12                                                       34.5         2.596   18                                                       37.4         2.403   2                                                        40.1         2.249   4                                                        42.7         2.120   3                                                        47.4         1.917   5                                                        51.8         1.764   9                                                        ______________________________________                                    

                  TABLE BB                                                        ______________________________________                                        (GaAPSO-20)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                        14.0         6.33    100                                                      19.8         4.48    33                                                       24.3         3.66    86                                                       28.2         3.17    16                                                       31.5         2.837   12                                                       34.7         2.589   14                                                       40.1         2.250   2                                                        42.7         2.118   2                                                        47.5         1.914   2                                                        52.0         1.759  
 6.                                                       ______________________________________                                    


9. The crystalline molecular sieves of claim 1 or 2 having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in Table C given in claim
 1. 10. Thecrystalline molecular sieves of claim 1 or 2 having a characteristicX-ray powder diffraction pattern which contains at least the d-spacingsset forth in Table D given in claim
 1. 11. The crystalline molecularsieves of claim 1 or 2 having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth in Table Egiven in claim
 1. 12. The crystalline molecular sieves of claim 1 or 2having a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth in Table F given in claim
 1. 13. Thecrystalline molecular sieves of claim 1 or 2 having a characteristicX-ray powder diffraction pattern which contains at least the d-spacingsset forth in Table G given in claim
 1. 14. The crystalline molecularsieves of claim 1 or 2 having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth in Table Hgiven in claim
 1. 15. The crystalline molecular sieves of claim 1 or 2having a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth in Table J given in claim
 1. 16. Thecrystalline molecular sieves of claim 1 or 2 having a characteristicX-ray powder diffraction pattern which contains at least the d-spacingsset forth in Table K given in claim
 1. 17. The crystalline molecularsieves of claim 1 or 2 having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth in Table Lgiven in claim
 1. 18. The crystalline molecular sieves of claim 17wherein the X-ray powder diffraction pattern set forth in Table Lcontains at least the d-spacings set forth in one of the followingTables LA and LB:

                  TABLE LA                                                        ______________________________________                                        (GaAPSO-34)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         9.5         9.30    100                                                      12.8         6.90    11                                                       14.1         6.29    9                                                        16.0         5.54    37                                                       18.0         4.93    10                                                       20.6         4.32    60                                                       22.2         4.00    2                                                        23.1         3.85    2                                                        25.2         3.53    13                                                       25.8         3.45    13                                                       27.6         3.23    3                                                        28.4         3.15    2                                                        29.5         3.03    3                                                        30.5         2.93    21                                                       31.3         2.861   15                                                       31.6         2.829   4                                                        32.3         2.768   2                                                        33.8         2.649   2                                                        34.4         2.609   6                                                        34.9         2.572   2                                                        36.1         2.490   2                                                        36.3         2.474   3                                                        38.7         2.330   2                                                        39.6         2.274   2                                                        43.1         2.100   2                                                        43.3         2.088   2                                                        47.6         1.912   2                                                        49.0         1.859   5                                                        50.1         1.820   1                                                        51.0         1.791   3                                                        53.1         1.725   2                                                        54.6         1.682  
 2.                                                       ______________________________________                                    

                  TABLE LB                                                        ______________________________________                                        (GaAPSO-34)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         9.6         9.17    100                                                      13.1         6.77    21                                                       14.1         6.27    3                                                        16.3         5.45    13                                                       18.0         4.93    8                                                        20.9         4.25    28                                                       22.4         3.97    3                                                        23.4         3.81    4                                                        25.2         3.53    7                                                        26.3         3.39    9                                                        28.1         3.17    5                                                        29.0         3.08    4                                                        30.0         2.980   3                                                        31.1         2.876   16                                                       31.4         2.845   9                                                        34.5         2.602   5                                                        35.0         2.565   5                                                        36.2         2.478  
 3.                                                       ______________________________________                                    


19. The crystalline molecular sieves of claim 1 or 2 having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in Table M given in claim
 1. 20. Thecrystalline molecular sieves of claim 19 wherein the X-ray powderdiffraction pattern set forth in Table M contains at least thed-spacings set forth in one of the following Tables MA and MB:

                  TABLE MA                                                        ______________________________________                                        (GaAPSO-35)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         8.7         10.21   20                                                       11.0         8.03    49                                                       11.8         7.48    3                                                        13.4         6.63    30                                                       15.9         5.57    9                                                        17.3         5.11    70                                                       17.9         4.96    17                                                       20.8         4.26    15                                                       21.2         4.19    55                                                       21.9         4.05    100                                                      23.2         3.83    18                                                       23.7         3.75    8                                                        25.1         3.54    5                                                        26.9         3.32    20                                                       27.4         3.26    2                                                        28.6         3.12    23                                                       28.8         3.10    23                                                       31.3         2.857   2                                                        32.1         2.787   46                                                       34.7         2.584   9                                                        35.0         2.563   3                                                        35.7         2.512   5                                                        37.8         2.383   2                                                        39.3         2.290   3                                                        42.2         2.141   5                                                        42.5         2.128   4                                                        43.2         2.094   4                                                        44.5         2.034   2                                                        48.6         1.873   9                                                        49.5         1.843   6                                                        51.6         1.772   7                                                        55.3         1.661   6                                                        ______________________________________                                    

                  TABLE MB                                                        ______________________________________                                        (GaAPSO-35)                                                                                        Relative Intensity                                       2θ     d(Å)                                                                              100 × I/I.sub.o                                    ______________________________________                                         8.5         10.4    8                                                         8.7         10.1    22                                                       11.0         8.02    100                                                      13.0         6.81    5                                                        13.5         6.54    81                                                       16.1         5.51    5                                                        17.5         5.08    35                                                       21.0         4.22    35                                                       21.6         4.11    5                                                        22.2         4.01    72                                                       23.0         3.86    5                                                        23.5         3.78    19                                                       25.1         3.55    15                                                       26.0         3.427   7                                                        26.6         3.352   4                                                        27.2         3.274   20                                                       28.6         3.125   43                                                       29.5         3.03    11                                                       31.7         2.827   5                                                        32.5         2.752   32                                                       34.6         2.593   8                                                        35.3         2.539   5                                                        36.3         2.476   4                                                        42.2         2.142   4                                                        43.1         2.101   5                                                        50.2         1.819   4                                                        51.8         1.765  
 4.                                                       ______________________________________                                    


21. The crystalline molecular sieves of claim 1 or 2 having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in Table N given in claim
 1. 22. Thecrystalline molecular sieves of claim 1 or 2 having a characteristicX-ray powder diffraction pattern which contains at least the d-spacingsset forth in Table 0 given in claim
 1. 23. The crystalline molecularsieves of claim 1 or 2 having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth in Table Pgiven in claim
 1. 24. The crystalline molecular sieves of claim 1 or 2having a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth in Table Q given in claim
 1. 25. Thecrystalline molecular sieves of claim 1 or 2 having a characteristicX-ray powder diffraction pattern which contains at least the d-spacingsset forth in Table R given in claim
 1. 26. The crystalline molecularsieves of claim 1 or 2 having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth in Table Sgiven in claim
 1. 27. The crystalline molecular sieves of claim 1 or 2having a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth in Table T given in claim
 1. 28. Thecrystalline molecular sieves of claim 1 or 2 having a characteristicX-ray powder diffraction pattern which contains at least the d-spacingsset forth in Table U given in claim
 1. 29. The crystalline molecularsieves of claim 1 or 2 having a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth in Table Vgiven in claim
 1. 30. The crystalline molecular sieves of claim 1 or 2having a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth in Table W given in claim
 1. 31. Thecrystalline molecular sieves of claim 1 or 2 having a characteristicX-ray powder diffraction pattern which contains at least the d-spacingsset forth in Table X given in claim
 1. 32. The crystalline molecularsieves of claim 31 wherein the X-ray powder diffraction pattern setforth in Table X contains at least the d-spacings set forth in thefollowing Table XA:

                  TABLE XA                                                        ______________________________________                                        (GaAPSO-26)                                                                                       Relative Intensity                                        2θ    d(Å)                                                                              100 × I/I.sub.o                                     ______________________________________                                         8.2        10.7    100                                                       10.5        8.45    3                                                         15.2        5.84    12                                                        17.3        5.13    6                                                         17.7        5.00    8                                                         19.5        4.54    5                                                         21.8        4.07    11                                                        22.4        3.96    16                                                        24.2        3.67    2                                                         24.8        3.59    4                                                         27.0        3.31    6                                                         27.6        3.23    2                                                         28.5        3.13    4                                                         29.2        3.06    3                                                         29.9        2.99    3                                                         30.4        2.94    *                                                         31.2        2.87    *                                                         31.7        2.822   7                                                         33.7        2.663   5                                                         34.4        2.606   3                                                         34.9        2.571   1                                                         36.4        2.467   4                                                         38.2        2.355   3                                                         47.5        1.912   3                                                         ______________________________________                                    


33. Process for preparing crystalline molecular sieves havingthree-dimensional microporous framework structures of GaO₂, AlO₂, PO₂and SiO₂ tetrahedral units having an empirical chemical composition onan anhydrous basis expressed by the formula:

    mR:(Ga.sub.w Al.sub.x p.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of gallium, aluminum, phosphorus and silicon respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D, and E of FIG. 1, said crystalline molecular sieves having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in one of the following Tables A to H and J toX:

                  TABLE A                                                         ______________________________________                                        (GaAPSO-5)                                                                    2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-7.7      12.28-11.48                                                                             m-vs                                                   19.4-19.9    4.58-4.46 w-m                                                    20.85-21.3   4.26-4.17 w-vs                                                   22.1-22.6    4.02-3.93 m-vs                                                   25.6-26.2    3.480-3.402                                                                             vw-m                                                   ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        (GaAPSO-11)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.8-8.2      11.19-10.85                                                                             m-s .sup.                                              9.0-9.8      9.83-9.03 vw-vs .sup.                                            12.8-13.6    6.92-6.51 vw-m                                                   19.9-20.5    4.46-4.33 m-s .sup.                                              20.8-21.8    4.27-4.08 m-vs                                                   22.0-22.6    4.04-3.93 m-vs                                                   22.6-23.1    3.93-3.85 vw-vs .sup.                                            23.1-23.5    3.85-3.79 w-vs                                                   ______________________________________                                    

                  TABLE C                                                         ______________________________________                                        (GaAPSO-14)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                         8.6-8.9     10.3-9.93                                                                              vs                                                      13.0         6.81     w                                                       21.9-22.2    4.06-4.00                                                                              w                                                       25.4         3.51     w                                                       27.5         3.24     w                                                       29.7         3.01     w                                                       ______________________________________                                    

                  TABLE D                                                         ______________________________________                                        (GaAPSO-16)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        11.3-11.6    7.83-7.63  w-vs                                                  18.55-18.9   4.78-4.70 vw-m .sup.                                             21.85-22.2   4.07-4.00  m-vs                                                  22.8-23.3    3.900-3.818                                                                             w-m                                                    26.4-27.3    3.370-3.267                                                                             w-m                                                    29.6-29.9    3.018-2.988                                                                             w-m                                                    ______________________________________                                    

                  TABLE E                                                         ______________________________________                                        (GaAPSO-17)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.70-7.75    11.5-11.4 vs                                                     13.4         6.61       s-vs                                                   15.5-15.55  5.72-5.70 s                                                      19.65-19.7   4.52-4.51 w-s                                                    20.5-20.6    4.33-4.31 vs                                                     31.8-32.0    2.812-2.797                                                                             w-s                                                    ______________________________________                                    

                  TABLE F                                                         ______________________________________                                        (GaAPSO-18)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                         9.6-9.65    9.21-9.16 vs                                                      15.5-15.55  5.72-5.70 m                                                      16.9-17.1    5.25-5.19 m                                                      20.15-20.25  4.41-4.39 m                                                      20.95-21.05  4.24-4.22 m                                                      31.8-32.5    2.814-2.755                                                                             m                                                      ______________________________________                                    

                  TABLE G                                                         ______________________________________                                        (GaASPO-20)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.8-14.2    6.42-6.23 m-vs                                                    19.6-20.15  6.53-4.41 m                                                      24.1-24.8    3.695-3.603                                                                             m-vs                                                   27.9-28.6    3.198-3.121                                                                             w                                                      31.3-32.1    2.861-2.791                                                                             w                                                      34.35-35.0   2.610-2.601                                                                             w-m                                                    ______________________________________                                    

                  TABLE H                                                         ______________________________________                                        (GaAPSO-31)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.4-9.5      10.53-9.31                                                                              w-s                                                    20.2-20.4    4.40-4.35 m                                                      22.0-22.1    4.040-4.022                                                                             m                                                      22.5-22.7    3.952-3.92                                                                              vs                                                     31.6-31.8    2.831-2.814                                                                             w-m                                                    ______________________________________                                    

                  TABLE J*                                                        ______________________________________                                        (GaAPSO-33)                                                                   2θ      d(Å) Relative Intensity                                     ______________________________________                                        9.25-9.55     9.56-9.26                                                                              w-m                                                    12.5-12.9     7.08-6.86                                                                              vs                                                     16.9-17.3     5.25-5.13                                                                              w-m                                                    20.45-20.9    4.34-4.25                                                                              w-m                                                    23.85-24.25   3.73-3.67                                                                              w-m                                                    26.05-26.35   3.42-3.38                                                                              w-m                                                    27.3-27.6     3.27-3.23                                                                              vs                                                     ______________________________________                                         *as-synthesized form                                                     

                  TABLE K*                                                        ______________________________________                                         (GaAPSO-33)                                                                  2θ      d(Å) Relative Intensity                                     ______________________________________                                        13.15-13.4    6.73-6.61                                                                              vs                                                     18.05-18.35   4.91-4.83                                                                              m                                                      18.4-18.6     4.82-4.77                                                                              m                                                      26.55-26.7    3.36-3.34                                                                              m                                                      32.0-32.1     2.80-2.79                                                                              m                                                      ______________________________________                                         *calcined form                                                           

                  TABLE L                                                         ______________________________________                                        (GaAPSO-34)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.3-9.8      9.51-9.03   m-vs                                                 12.6-13.2    7.03-6.71  .sup. w-m                                             15.8-16.3    5.61-5.44 vw-m                                                   20.25-21.2   4.39-4.19   w-vs                                                 24.8-25.4     3.59-3.507                                                                             vw-m                                                   30.0-30.9    2.979-2.894                                                                             vw-m                                                   ______________________________________                                    

                  TABLE M                                                         ______________________________________                                        (GaAPSO-35)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        10.6-11.1    8.35-7.97 vw-vs                                                  13.1-13.7    6.76-6.46 vw-vs                                                  17.0-17.6    5.22-5.04 w-s                                                    20.6-21.6    4.31-4.11 vw-m                                                   21.6-22.3    4.11-3.99 .sup.  m-vs                                            28.1-28.8    3.175-3.100                                                                             vw-m                                                   ______________________________________                                    

                  TABLE N                                                         ______________________________________                                        (GaAPSO-36)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.45-8.0     11.14-11.05                                                                             vs                                                     8.1-8.3      10.91-10.65                                                                             w-m                                                    16.3-16.6    5.44-5.34 w-m                                                    18.9-19.4    4.70-4.57 w-m                                                    20.7-21.0    4.29-4.23 w-m                                                    ______________________________________                                    

                  TABLE O                                                         ______________________________________                                        (GaAPSO-37)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        6.1-6.3      14.49-14.03                                                                             vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE P                                                         ______________________________________                                        (GaAPSO-39)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m                                                      13.1-13.5    6.76-6.56 m                                                      17.8-18.4    4.98-4.82 w-m                                                    20.8-21.3    4.27-4.17  m-vs                                                   22.2-22.85   4.00-3.892                                                                              m-vs                                                   26.4-27.05  3.376-3.296                                                                             w-m                                                    ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (GaAPSO-40)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.5-7.7      11.79-11.48                                                                             vw-m .sup.                                             8.0-8.1      11.05-10.94                                                                             .sup.  s-vs                                            12.4-12.5    7.14-7.08  w-vs                                                  13.6-13.8    6.51-6.42 m-s                                                    14.0-14.1    6.33-6.28 w-m                                                    27.8-28.0    3.209-3.187                                                                             w-m                                                    ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (GaAPSO-41)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.6-13.8    6.51-6.42 w-m                                                    20.5-2.6     4.33-4.31 w-m                                                    21.1-21.3    4.21-4.17 vs                                                     22.1-22.3    4.02-3.99 m-s                                                    22.8-23.0    3.90-3.86 m                                                      23.1-23.4    3.82-3.80 w-m                                                    25.5-25.9    3.493-3.44                                                                              w-m                                                    ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (GaAPSO-42)                                                                   2θ      d(Å)  Relative Intensity                                    ______________________________________                                        7.15-7.4      12.36-11.95                                                                              .sup. m-vs                                            12.5-12.7    7.08-6.97 m-s                                                   21.75-21.9    4.09-4.06 m-s                                                    24.1-24.25   3.69-3.67 vs                                                    27.25-27.4    3.273-3.255                                                                             s                                                      30.05-30.25  2.974-2.955                                                                             m-s                                                   ______________________________________                                    

                  TABLE T                                                         ______________________________________                                        (GaAPSO-43)                                                                   2θ      d(Å)  Relative Intensity                                    ______________________________________                                        12.3-12.95    7.20-6.83 m-vs                                                  16.8-17.45    5.28-5.09 vw-w                                                  21.45-21.85   4.145-4.071                                                                             m-vs                                                  27.1-27.85    3.291-3.232                                                                             w-vs                                                  32.4-33.2     2.763-2.699                                                                             vw-m                                                  ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (GaAPSO-44)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m-vs                                                   15.9-16.3    5.57-5.44 vw-m                                                   20.5-21.0    4.33-4.23 m-vs                                                   24.3-25.1     3.66-3.548                                                                             w-m                                                    30.5-31.1    2.931-2.876                                                                             vw-m                                                   ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        (GaAPSO-46)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-8.1      12.28-10.92                                                                             vs                                                     12.9-13.6    6.86-6.51 vw                                                     21.2-22.2     4.19-4.501                                                                             vw-m                                                    22.5-23.45   3.95-3.793                                                                             vw-m                                                   26.6-27.9    3.351-3.198                                                                             vw-m                                                   ______________________________________                                    

                  TABLE W                                                         ______________________________________                                        (GaAPSO-47)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.4-9.6      9.41-9.21 vs                                                     12.8-13.1    6.92-6.76 vw-m                                                   16.0-16.3    5.54-5.44 vw-m                                                   20.5-21.0    4.31-4.23   m-vs                                                 24.6-25.3    3.613-3.526                                                                             vw-m                                                   30.6-31.1    2.921-2.876                                                                             vw-m                                                   ______________________________________                                    

                  TABLE X                                                         ______________________________________                                        (GaPSO-26)                                                                    2θ     d(Å) Relative Intensity                                      ______________________________________                                         8.2         10.8-10.7                                                                              vs                                                      10.5-10.6    8.45-8.42                                                                              vw-w                                                    15.2         5.84     w                                                       17.7-17.8    5.00-4.99                                                                              vw-w                                                    21.8         4.07     w                                                       22.4         3.97-3.96                                                                                w-m,                                                  ______________________________________                                    

said process comprising providing a reaction mixture composition at aneffective temperature and for an effective time sufficient to producesaid molecular sieves, said reaction mixture composition being expressedin terms of molar oxide ratios as follows:

    aR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of "R" andis an effective amount greater than zero to about 6; "b" has a value offrom zero to about 500; and "w", "x", "y" and "z" represent the molefractions, respectively, of gallium, aluminum, phosphorus and silicon inthe (Ga_(w) Al_(x) P_(y) Si_(z))O₂ constituent, and each has a value ofat least 0.01.
 34. Process according to claim 33 wherein "w", "x", "y"and "z" are within the area defined by points F, G, H, I and J of FIG.3.
 35. Process according to claim 33 wherein "a" is not greater thanabout 1.0.
 36. Process according to claim 33 wherein "b" is from about 2to about
 500. 37. Process according to claim 36 wherein "b" is fromabout 2 to about
 300. 38. Process according to claim 37 wherein "b" isnot greater than about
 20. 39. Process according to claim 33 wherein thereaction mixture composition contains from about 0.5 to about 1.0 totalmoles of gallium and silicon per mole of phosphorus.
 40. Processaccording to claim 33 wherein the reaction mixture composition containsfrom about 0.75 to about 1.25 moles of aluminum per mole of phosphorus.41. Process according to claim 33 wherein the source of phosphorus inthe reaction mixture is orthophosphoric acid.
 42. Process according toclaim 33 wherein the source of phosphorus in the reaction mixture isorthophosphoric acid and the source of aluminum is at least one compoundselected from the group consisting of pseudo-boehmite and aluminumalkoxides.
 43. Process according to claim 42 wherein the aluminumalkoxide is aluminum isopropoxide.
 44. Process according to claim 33wherein the silicon source is silica.
 45. Process according to claim 33wherein the silica source is a tetraalkyl orthosilicate.
 46. Processaccording to claim 33 wherein the source of gallium is selected from thegroup consisting of oxides, hydroxides, alkoxides, chlorides, bromides,iodides, sulfates, nitrates, carboxylates and mixtures thereof. 47.Process according to claim 33 wherein the organic templating agent is aquanternary ammonium or quaternary phosphonium compound having theformula:

    R.sub.4 X.sup.+

wherein X is nitrogen or phosphorus and each R is an alkyl or aryl groupcontaining from 1 to 8 carbon atoms.
 48. Process according to claim 33wherein the organic templating agent is an amine.
 49. Process accordingto claim 33 wherein the templating agent is selected from the groupconsisting of tetrapropylammonium ion; tetraethylammonium ion;tripropylamine; triethylamine; triethanolamine; piperidine;cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine;N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine;1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine;N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammoniumion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone;di-n-propylamine; and a polymeric quaternary ammonium salt [(C₁₄ H₃₂N₂)(OH)₂ ]_(x) wherein x is a value of a least
 2. 50. Molecular sievesprepared by calcining, at a temperature sufficiently high to remove atleast some of any organic templating agent present in theintracrystalline pore system, the crystalline molecular sieves havingthree-dimensional microporous framework structures of GaO₂, AlO₂, PO₂and SiO₂ tetrahedral units having an empirical chemical composition onan anhydrous basis expressed by the formula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of gallium, aluminum, phosphorus and silicon respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D, and E of FIG. 1, said crystalline molecular sieves having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in one of the following Tables A to H and J toX:

                  TABLE A                                                         ______________________________________                                        (GaAPSO-5)                                                                    2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-7.7      12.28-11.48                                                                             m-vs                                                   19.4-19.9    4.58-4.46 w-m                                                    20.85-21.3   4.26-4.17 w-vs                                                   22.1-22.6    4.02-3.93 m-vs                                                   25.6-26.2    3.480-3.402                                                                             vw-m                                                   ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        (GaAPSO-11)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.8-8.2      11.19-10.85                                                                             m-s .sup.                                              9.0-9.8      9.83-9.03 vw-vs .sup.                                            12.8-13.6    6.92-6.51 vw-m                                                   19.9-20.5    4.46-4.33 m-s .sup.                                              20.8-21.8    4.27-4.08 m-vs                                                   22.0-22.6    4.04-3.93 m-vs                                                   22.6-23.1    3.93-3.85 vw-vs .sup.                                            23.1-23.5    3.85-3.79 w-vs                                                   ______________________________________                                    

                  TABLE C                                                         ______________________________________                                        (GaAPSO-14)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                         8.6-8.9     10.3-9.93                                                                              vs                                                      13.0         6.81     w                                                       21.9-22.2    4.06-4.00                                                                              w                                                       25.4         3.51     w                                                       27.5         3.24     w                                                       29.7         3.01     w                                                       ______________________________________                                    

                  TABLE D                                                         ______________________________________                                        (GaAPSO-16)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        11.3-11.6    7.83-7.63  w-vs                                                  18.55-18.9   4.78-4.70 vw-m .sup.                                             21.85-22.2   4.07-4.00  m-vs                                                  22.8-23.3    3.900-3.818                                                                             w-m                                                    26.4-27.3    3.370-3.267                                                                             w-m                                                    29.6-29.9    3.018-2.988                                                                             w-m                                                    ______________________________________                                    

                  TABLE E                                                         ______________________________________                                        (GaAPSO-17)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.70-7.75    11.5-11.4 vs                                                     13.4         6.61       s-vs                                                   15.5-15.55  5.72-5.70 s                                                      19.65-19.7   4.52-4.51 w-s                                                    20.5-20.6    4.33-4.31 vs                                                     31.8-32.0    2.812-2.797                                                                             w-s                                                    ______________________________________                                    

                  TABLE F                                                         ______________________________________                                        (GaAPSO-18)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                         9.6-9.65    9.21-9.16 vs                                                      15.5-15.55  5.72-5.70 m                                                      16.9-17.1    5.25-5.19 m                                                      20.15-20.25  4.41-4.39 m                                                      20.95-21.05  4.24-4.22 m                                                      31.8-32.5    2.814-2.755                                                                             m                                                      ______________________________________                                    

                  TABLE G                                                         ______________________________________                                        (GaASPO-20)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.8-14.2    6.42-6.23 m-vs                                                    19.6-20.15  6.53-4.41 m                                                      24.1-24.8    3.695-3.603                                                                             m-vs                                                   27.9-28.6    3.198-3.121                                                                             w                                                      31.3-32.1    2.861-2.791                                                                             w                                                      34.35-35.0   2.610-2.601                                                                             w-m                                                    ______________________________________                                    

                  TABLE H                                                         ______________________________________                                        (GaAPSO-31)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.4-9.5      10.53-9.31                                                                              w-s                                                    20.2-20.4    4.40-4.35 m                                                      22.0-22.1    4.040-4.022                                                                             m                                                      22.5-22.7    3.952-3.92                                                                              vs                                                     31.6-31.8    2.831-2.814                                                                             w-m                                                    ______________________________________                                    

                  TABLE J*                                                        ______________________________________                                        (GaAPSO-33)                                                                   2θ      d(Å) Relative Intensity                                     ______________________________________                                        9.25-9.55     9.56-9.26                                                                              w-m                                                    12.5-12.9     7.08-6.86                                                                              vs                                                     16.9-17.3     5.25-5.13                                                                              w-m                                                    20.45-20.9    4.34-4.25                                                                              w-m                                                    23.85-24.25   3.73-3.67                                                                              w-m                                                    26.05-26.35   3.42-3.38                                                                              w-m                                                    27.3-27.6     3.27-3.23                                                                              vs                                                     ______________________________________                                         *as-synthesized form                                                     

                  TABLE K*                                                        ______________________________________                                         (GaAPSO-33)                                                                  2θ      d(Å) Relative Intensity                                     ______________________________________                                        13.15-13.4    6.73-6.61                                                                              vs                                                     18.05-18.35   4.91-4.83                                                                              m                                                      18.4-18.6     4.82-4.77                                                                              m                                                      26.55-26.7    3.36-3.34                                                                              m                                                      32.0-32.1     2.80-2.79                                                                              m                                                      ______________________________________                                         *calcined form                                                           

                  TABLE L                                                         ______________________________________                                        (GaAPSO-34)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.3-9.8      9.51-9.03   m-vs                                                 12.6-13.2    7.03-6.71  .sup. w-m                                             15.8-16.3    5.61-5.44 vw-m                                                   20.25-21.2   4.39-4.19   w-vs                                                 24.8-25.4     3.59-3.507                                                                             vw-m                                                   30.0-30.9    2.979-2.894                                                                             vw-m                                                   ______________________________________                                    

                  TABLE M                                                         ______________________________________                                        (GaAPSO-35)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        10.6-11.1    8.35-7.97 vw-vs                                                  13.1-13.7    6.76-6.46 vw-vs                                                  17.0-17.6    5.22-5.04 w-s                                                    20.6-21.6    4.31-4.11 vw-m                                                   21.6-22.3    4.11-3.99 .sup.  m-vs                                            28.1-28.8    3.175-3.100                                                                             vw-m                                                   ______________________________________                                    

                  TABLE N                                                         ______________________________________                                        (GaAPSO-36)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.45-8.0     11.14-11.05                                                                             vs                                                     8.1-8.3      10.91-10.65                                                                             w-m                                                    16.3-16.6    5.44-5.34 w-m                                                    18.9-19.4    4.70-4.57 w-m                                                    20.7-21.0    4.29-4.23 w-m                                                    ______________________________________                                    

                  TABLE O                                                         ______________________________________                                        (GaAPSO-37)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        6.1-6.3      14.49-14.03                                                                             vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE P                                                         ______________________________________                                        (GaAPSO-39)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m                                                      13.1-13.5    6.76-6.56 m                                                      17.8-18.4    4.98-4.82 w-m                                                    20.8-21.3    4.27-4.17  m-vs                                                   22.2-22.85   4.00-3.892                                                                              m-vs                                                   26.4-27.05  3.376-3.296                                                                             w-m                                                    ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (GaAPSO-40)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.5-7.7      11.79-11.48                                                                             vw-m .sup.                                             8.0-8.1      11.05-10.94                                                                             .sup.  s-vs                                            12.4-12.5    7.14-7.08  w-vs                                                  13.6-13.8    6.51-6.42 m-s                                                    14.0-14.1    6.33-6.28 w-m                                                    27.8-28.0    3.209-3.187                                                                             w-m                                                    ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (GaAPSO-41)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.6-13.8    6.51-6.42 w-m                                                    20.5-2.6     4.33-4.31 w-m                                                    21.1-21.3    4.21-4.17 vs                                                     22.1-22.3    4.02-3.99 m-s                                                    22.8-23.0    3.90-3.86 m                                                      23.1-23.4    3.82-3.80 w-m                                                    25.5-25.9    3.493-3.44                                                                              w-m                                                    ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (GaAPSO-42)                                                                   2θ      d(Å)  Relative Intensity                                    ______________________________________                                        7.15-7.4      12.36-11.95                                                                              .sup. m-vs                                            12.5-12.7    7.08-6.97 m-s                                                   21.75-21.9    4.09-4.06 m-s                                                    24.1-24.25   3.69-3.67 vs                                                    27.25-27.4    3.273-3.255                                                                             s                                                      30.05-30.25  2.974-2.955                                                                             m-s                                                   ______________________________________                                    

                  TABLE T                                                         ______________________________________                                        (GaAPSO-43)                                                                   2θ      d(Å)  Relative Intensity                                    ______________________________________                                        12.3-12.95    7.20-6.83 m-vs                                                  16.8-17.45    5.28-5.09 vw-w                                                  21.45-21.85   4.145-4.071                                                                             m-vs                                                  27.1-27.85    3.291-3.232                                                                             w-vs                                                  32.4-33.2     2.763-2.699                                                                             vw-m                                                  ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (GaAPSO-44)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m-vs                                                   15.9-16.3    5.57-5.44 vw-m                                                   20.5-21.0    4.33-4.23 m-vs                                                   24.3-25.1     3.66-3.548                                                                             w-m                                                    30.5-31.1    2.931-2.876                                                                             vw-m                                                   ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        (GaAPSO-46)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-8.1      12.28-10.92                                                                             vs                                                     12.9-13.6    6.86-6.51 vw                                                     21.2-22.2     4.19-4.501                                                                             vw-m                                                    22.5-23.45   3.95-3.793                                                                             vw-m                                                   26.6-27.9    3.351-3.198                                                                             vw-m                                                   ______________________________________                                    

                  TABLE W                                                         ______________________________________                                        (GaAPSO-47)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.4-9.6      9.41-9.21 vs                                                     12.8-13.1    6.92-6.76 vw-m                                                   16.0-16.3    5.54-5.44 vw-m                                                   20.5-21.0    4.31-4.23   m-vs                                                 24.6-25.3    3.613-3.526                                                                             vw-m                                                   30.6-31.1    2.921-2.876                                                                             vw-m                                                   ______________________________________                                    

                  TABLE X                                                         ______________________________________                                        (GaAPSO-26)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                         8.2         10.8-10.7                                                                              vs                                                      10.5-10.6    8.45-8.42                                                                              vw-w                                                    15.2         5.84     w                                                       17.7--17.8   5.00-4.99                                                                              vw-w                                                    21.8         4.07     w                                                       22.4         3.97-3.96                                                                                w-m.                                                  ______________________________________                                    


51. Crystalline molecular sieves having three-dimensional microporousframework structures of GaO₂, AlO₂, PO₂ and SiO₂ tetrahedral unitshaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of gallium, aluminum, phosphorus and silicon respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D, and E of FIG.
 1. 52. Crystalline molecular sieves according to claim51 wherein the mole fractions of gallium, aluminum, phosphorus andsilicon present as tetrahedral oxides are within the hexagonalcompositional area defined by points a, b, c, d, e and f of FIG.
 2. 53.Crystalline molecular sieves according to claim 52 wherein the molefractions of gallium, aluminum, phosphorus and silicon present astetrahedral oxides are within the hexagonal compositional area definedby points g, h, i, j, k and l of FIG.
 2. 54. The crystalline molecularsieves of claim 51 or 52 wherein "m" is not greater than about 0.2. 55.Process for preparing crystalline molecular sieves havingthree-dimensional microporous framework structures of GaO₂, AlO₂, PO₂and SiO₂ tetrahedral units having an empirical chemical composition onan anhydrous basis expressed by the formula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of gallium, aluminum, phosphorus and silicon respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D, and E of FIG. 1, wherein the process comprises providing a reactionmixture composition at an effective temperature and for an effectivetime sufficient to produce said molecular sieves, said reaction mixturecomposition being expressed in terms of molar oxide ratios as follows:

    aR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of "R" andis an effective amount greater than zero to about 6; "b" has a value offrom zero to about 500; and "w", "x", "y" and "z" represent the molefractions, respectively, of gallium, aluminum, phosphorus and silicon inthe (Ga_(w) Al_(x) P_(y) Si_(z))O₂ constituent, and each has a value ofat least 0.01.
 56. Process according to claim 55 wherein "w", "x", "y"and "z" are within the area defined by points F, G, H, I and J of FIG.3.
 57. Process according to claim 55 wherein "a" is not greater thanabout 1.0.
 58. Process according to claim 55 wherein "b" is from about 2to about
 500. 59. Process according to claim 58 wherein "b" is fromabout 2 to about
 300. 60. Process according to claim 59 wherein "b" isnot greater than about
 20. 61. Process according to claim 55 wherein thereaction mixture composition contains from about 0.5 to about 1.0 totalmoles of gallium and silicon per mole of phosphorus.
 62. Processaccording to claim 55 wherein the reaction mixture composition containsfrom about 0.75 to about 1.25 moles of aluminum per mole of phosphorus.63. Process according to claim 55 wherein the source of phosphorus inthe reaction mixture is orthophosphoric acid.
 64. Process according toclaim 55 wherein the source of phosphorus in the reaction mixture isorthophosphoric acid and the source of aluminum is at least one compoundselected from the group consisting of pseudo-boehmite and aluminumalkoxide.
 65. Process according to claim 64 wherein the aluminumalkoxide is aluminum isopropoxide.
 66. Process according to claim 55wherein the silicon source is silica.
 67. Process according to claim 55wherein the silicon source is a tetraalkyl orthosilicate.
 68. Processaccording to claim 55 wherein the source of gallium is selected from thegroup consisting of oxides, hydroxides, alkoxides, chlorides, bromides,iodides, sulfates, nitrates, carboxylates and mixtures thereof. 69.Process according to claim 55 wherein the organic templating agent is aquaternary ammonium or quanternary phosphonium compound having theformula:

    R.sub.4 X.sup.+

wherein X is nitrogen or phosphorus and each R is an alkyl or aryl groupcontaining from 1 to 8 carbon atoms.
 70. Process according to claim 55wherein the organic templating agent is an amine.
 71. Process accordingto claim 55 wherein the templating agent is selected from the groupconsisting of tetrapropylammonium ion; tetraethylammonium ion;tripropylamine; triethylamine; triethanolamine; piperidine;cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine;N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine;1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine;N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammoniumion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone;di-n-propylamine; and a polymeric quanternary ammonium salt [(C₁₄ H₃₂N₂)(OH)₂ ]_(x) wherein x has a value of at least
 2. 72. Molecular sievesprepared by calcining, at a temperature sufficiently high to remove atleast some of any organic templating agent present in theintracrystalline pore system, the crystalline molecular sieves havingthree-dimensional microporous framework structures of GaO₂, AlO₂, PO₂and SiO₂ tetrahedral units having an empirical chemical composition onan anhydrous basis expressed by the formula:

    mR:(Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of gallium, aluminum, phosphorus and silicon respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D, and E of FIG. 1.